First-Principles Study of Microscopic Electrochemistry at the LiCoO2 Cathode/LiNbO3 Coating/β-Li3PS4 Solid Electrolyte Interfaces in an All-Solid-State BatteryClick to copy article linkArticle link copied!
- Bo Gao*Bo Gao*Email: [email protected]Center for Green Research on Energy and Environmental Materials (GREEN) and International Center for Materials Nanoarchitectonics (MANA), NIMS, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, JapanMore by Bo Gao
- Randy JalemRandy JalemCenter for Green Research on Energy and Environmental Materials (GREEN) and International Center for Materials Nanoarchitectonics (MANA), NIMS, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, JapanElements Strategy Initiative for Catalysts & Batteries, Kyoto University, 1-30 Goryo-Ohara, Nishikyo-ku, Kyoto 615-8245, JapanPRESTO, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama 333-0012, JapanMore by Randy Jalem
- Yoshitaka Tateyama*Yoshitaka Tateyama*Email: [email protected]Center for Green Research on Energy and Environmental Materials (GREEN) and International Center for Materials Nanoarchitectonics (MANA), NIMS, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, JapanElements Strategy Initiative for Catalysts & Batteries, Kyoto University, 1-30 Goryo-Ohara, Nishikyo-ku, Kyoto 615-8245, JapanMore by Yoshitaka Tateyama
Abstract
High interfacial resistance between electrode and solid electrolyte (SE) is one of the major challenges for the commercial application of all-solid-state batteries (ASSBs), and coating at the interface is an effective way for decreasing the resistance. However, microscopic electrochemistry especially for the electrochemical potential and the distribution of Li+ at the interface has not been well established yet, impeding the in-depth understanding of interfacial Li+ transport. Herein, we have introduced a potential energy profile for Li+, ηLi+, and demonstrated that the interfacial ηLi+ can be evaluated from the calculated interfacial Li vacancy formation energy or the bulk vacancy formation energy and the interface band alignment. Through computational analysis of the representative LiCoO2 cathode/LiNbO3 coating/β-Li3PS4 SE interfaces using the novel interface structure prediction scheme based on the CALYPSO method, we found that ηLi+ at the LiCoO2/β-Li3PS4 interface is highly disordered under the influence of the interface reconstruction and is rather electronic conductive. Insertion of LiNbO3 coating can effectively decrease the preference of ion mixing. Besides, the appropriate changes in band alignments lead to a decrease of difference in the interfacial ηLi+ and lower resistances at the interfaces. The results provide a reliable explanation for the effectiveness of the coating layer observed experimentally. Furthermore, our study provides a guidance for the future simulation of the microscopic electrochemistry at the electrode/SE interfaces in ASSBs.
This publication is licensed under
License Summary*
You are free to share(copy and redistribute) this article in any medium or format within the parameters below:
Creative Commons (CC): This is a Creative Commons license.
Attribution (BY): Credit must be given to the creator.
Non-Commercial (NC): Only non-commercial uses of the work are permitted.
No Derivatives (ND): Derivative works may be created for non-commercial purposes, but sharing is prohibited.
*Disclaimer
This summary highlights only some of the key features and terms of the actual license. It is not a license and has no legal value. Carefully review the actual license before using these materials.
License Summary*
You are free to share(copy and redistribute) this article in any medium or format within the parameters below:
Creative Commons (CC): This is a Creative Commons license.
Attribution (BY): Credit must be given to the creator.
Non-Commercial (NC): Only non-commercial uses of the work are permitted.
No Derivatives (ND): Derivative works may be created for non-commercial purposes, but sharing is prohibited.
*Disclaimer
This summary highlights only some of the key features and terms of the actual license. It is not a license and has no legal value. Carefully review the actual license before using these materials.
License Summary*
You are free to share(copy and redistribute) this article in any medium or format within the parameters below:
Creative Commons (CC): This is a Creative Commons license.
Attribution (BY): Credit must be given to the creator.
Non-Commercial (NC): Only non-commercial uses of the work are permitted.
No Derivatives (ND): Derivative works may be created for non-commercial purposes, but sharing is prohibited.
*Disclaimer
This summary highlights only some of the key features and terms of the actual license. It is not a license and has no legal value. Carefully review the actual license before using these materials.
License Summary*
You are free to share(copy and redistribute) this article in any medium or format within the parameters below:
Creative Commons (CC): This is a Creative Commons license.
Attribution (BY): Credit must be given to the creator.
Non-Commercial (NC): Only non-commercial uses of the work are permitted.
No Derivatives (ND): Derivative works may be created for non-commercial purposes, but sharing is prohibited.
*Disclaimer
This summary highlights only some of the key features and terms of the actual license. It is not a license and has no legal value. Carefully review the actual license before using these materials.
License Summary*
You are free to share(copy and redistribute) this article in any medium or format within the parameters below:
Creative Commons (CC): This is a Creative Commons license.
Attribution (BY): Credit must be given to the creator.
Non-Commercial (NC): Only non-commercial uses of the work are permitted.
No Derivatives (ND): Derivative works may be created for non-commercial purposes, but sharing is prohibited.
*Disclaimer
This summary highlights only some of the key features and terms of the actual license. It is not a license and has no legal value. Carefully review the actual license before using these materials.
Introduction
Methodology
γf (eV/nm2) | |
---|---|
LCO(104)/LNO(11̅0) | |
IFpristine | 0 |
IFLCO,LNO | 1.29 |
IF2LCO,2LNO | 0.22 |
IF2LCO,3LNO | 1.02 |
IFCo–Nb | 1.02 |
LNO(11̅0)/LPS(010) | |
IFpristine | 0 |
IFLNO,LPS | –0.06 |
IF2LNO,2LPS | –0.19 |
IFNb–P | –1.31 |
IFNb(subsurface)–P | 0.54 |
IFNb–P(subsurface) | –0.41 |
IFO–S | 0.78 |



Results
Interface Stabilities and Structures
Figure 1
Figure 1. Predicted energetically low interface structures: IFpristine of the LCO(104)/LNO(11̅0) interface (a) and IFpristine (b) and IFNb–P (c) of the LNO(11̅0)/LPS(010) interface. The insets show the enlarged local geometries of the interface structures. The corresponding interface formation energies are listed in Table 1. The green, red, brown, blue, pink, and yellow balls represent the Li, O, Nb, Co, P, and S ions, respectively.
Li Vacancy Formation Energy
Figure 2
Electronic Densities of States
Figure 3
Figure 3. (Left panels) Calculated layer-decomposed PDOSs for IFpristine of the LCO(104)/LNO(11̅0) interface (a) and IFpristine (b) and IFNb–P (c) of the LNO(11̅0)/LPS(010) interface. The dashed line in each panel indicates the Fermi level. (Right panels) Corresponding layers in the interface models.
Discussion

Figure 4
Figure 4. Schematic illustrations of ηLi (green line), ηLi+ (black line) and ηe– (red line) in the cathode and SE bulks (a) and in the interface model (b) in ASSBs. Especially in the interface model, the electrons are redistributed at the interface, varying ηLi+ and ηe–. The calculations of Li vacancy formation energy with respect to the Li metal in the bulks and interface model are illustrated in (a,b) as well.



Figure 5
Figure 5. Calculated ηLi(interf) in the LCO(104)/LPS(010) (a,b), LCO(104)/LNO(11̅0) (c), and LNO(11̅0)/LPS(010) (d,e) interface models. In each figure, the black dots represent the directly calculated values shown in Figure 2. The solid lines refer to the values evaluated from eq 7. For comparison, the ηLi(bulk) is also plotted using dashed lines.

ΔηLi+(interf) (eV) | ΔηLi+(bulk) (eV) | |
---|---|---|
LCO(104)/LPS(010) IFpristine | 0.60 | 1.16 |
LCO(104)/LPS(010) IFCo–P,O–S | –0.35 | 1.16 |
LCO(104)/LNO(11̅0) IFpristine | –0.11 | 1.45 |
LNO(11̅0)/LPS(010) IFpristine | 0 | –0.29 |
LNO(11̅0)/LPS(010) IFNb–P | 0 | –0.29 |
Conclusions
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.0c19091.
Lattice parameters calculated in our work and identified in experiments of LCO, LPS, and LNO, selected superlattices for LCO(104)/LNO(11̅0), and LNO(11̅0)/LPS(010) interfaces singled out using the lattice matching algorithm in the CALYPSO methodology, interface formation energies of energetically favorable structures of LCO(104)/LPS(010) interfaces, calculated EF(interf) – ηe–(interf), ηLi(interf), Vi and Ve in the LCO(104)/LPS(010), LCO(104)/LNO(11̅0), and LNO(11̅0)/LPS(010) interfaces, calculated ηLi(bulk) and ηe–(bulk) in LCO, LPS and LNO bulks, predicted metastable structures of the LCO(104)/LNO(11̅0) interface, predicted metastable structures of the LNO(11̅0)/LPS(010) interface, calculated ηLi(interf) in the IFpristine and IFCo–P,O–S of the LCO(104)/LPS(010) interface, calculated layer-decomposed PDOSs for IFpristine and IFCo–P,O–S of the LCO(104)/LPS(010) interface, calculated the charge difference and its average value over the plane parallel to the interface in the IFpristine of LCO(104)/LNO(11̅0) interface, schematic illustrations of the ηLi+ and ηe– in the bulk and interface models for LCO(104)/LPS(010), LCO(104)/LNO(11̅0) and LNO(11̅0)/LPS(010) interfaces (PDF)
Terms & Conditions
Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.
Acknowledgments
This work was supported in part by JSPS KAKENHI grant number JP19H05815 and by MEXT as “Program for Promoting Researches on the Supercomputer Fugaku” (Fugaku Battery & Fuel Cell Project), grant number JPMXP1020200301, Elements Strategy Initiative, grant number JPMXP0112101003, Materials Processing Science project (“Materealize”), grant number JPMXP0219207397. The calculations were carried out on the supercomputers at NIMS, The University of Tokyo and Kyushu University. This research also used computational resources of supercomputer Fugaku provided by the RIKEN Center for Computational Science (project IDs: hp170054, hp180101, hp200131).
References
This article references 47 other publications.
- 1Famprikis, T.; Canepa, P.; Dawson, J. A.; Islam, M. S.; Masquelier, C. Fundamentals of Inorganic Solid-State Electrolytes for Batteries. Nat. Mater. 2019, 18, 1278– 1291, DOI: 10.1038/s41563-019-0431-3Google Scholar1Fundamentals of inorganic solid-state electrolytes for batteriesFamprikis, Theodosios; Canepa, Pieremanuele; Dawson, James A.; Islam, M. Saiful; Masquelier, ChristianNature Materials (2019), 18 (12), 1278-1291CODEN: NMAACR; ISSN:1476-1122. (Nature Research)A review. In the crit. area of sustainable energy storage, solid-state batteries have attracted considerable attention due to their potential safety, energy-d. and cycle-life benefits. This Review describes recent progress in the fundamental understanding of inorg. solid electrolytes, which lie at the heart of the solid-state battery concept, by addressing key issues in the areas of multiscale ion transport, electrochem. and mech. properties, and current processing routes. The main electrolyte-related challenges for practical solid-state devices include utilization of metal anodes, stabilization of interfaces and the maintenance of phys. contact, the solns. to which hinge on gaining greater knowledge of the underlying properties of solid electrolyte materials.
- 2Tian, Y.; Shi, T.; Richards, W. D.; Li, J.; Kim, J. C.; Bo, S.-H.; Ceder, G. Compatibility Issues between Electrodes and Electrolytes in Solid-State Batteries. Energy Environ. Sci. 2017, 10, 1150– 1166, DOI: 10.1039/C7EE00534BGoogle Scholar2Compatibility issues between electrodes and electrolytes in solid-state batteriesTian, Yaosen; Shi, Tan; Richards, William D.; Li, Juchuan; Kim, Jae Chul; Bo, Shou-Hang; Ceder, GerbrandEnergy & Environmental Science (2017), 10 (5), 1150-1166CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)Remarkable success has been achieved in the discovery of ceramic alkali superionic conductors as electrolytes in solid-state batteries; however, obtaining a stable interface between these electrolytes and electrodes is difficult. Only limited studies on the compatibility between electrodes and solid electrolytes have been reported, partially because of the need for expensive instrumentation and special cell designs. Without simple yet powerful tools, these compatibility issues cannot be systematically investigated, thus hindering the generalization of design rules for the integration of solid-state battery components. Herein, we present a methodol. that combines d. functional theory calcns. and simple exptl. techniques such as X-ray diffraction, simultaneous differential scanning calorimetry and thermal gravimetric anal., and electrochem. to efficiently screen the compatibility of numerous electrode/electrolyte pairs. We systemically distinguish between the electrochem. stability of the solid-state conductor, which is relevant wherever the electrolyte contacts an electron pathway, and the electrochem. stability of the electrode/electrolyte interfaces. For the solid electrolyte, we are able to computationally derive an abs. thermodn. stability voltage window, which is small for Na3PS4 and Na3PSe4, and a larger voltage window which can be kinetically stabilized. The exptl. stability, when measured with reliable techniques, falls between these thermodn. and kinetic limits. Employing a Na solid-state system as an example, we demonstrate the efficiency of our method by finding the most stable system (NaCrO2|Na3PS4|Na-Sn) within a selected chem. space (more than 20 different combinations of electrodes and electrolytes). Important selection criteria for the cathode, electrolyte, and anode in solid-state batteries are also derived from this study. The current method not only provides an essential guide for integrating all-solid-state battery components but can also significantly accelerate the expansion of the electrolyte/electrode compatibility data.
- 3Manthiram, A.; Yu, X.; Wang, S. Lithium Battery Chemistries Enabled by Solid-State Electrolytes. Nat. Rev. Mater. 2017, 2, 16103, DOI: 10.1038/natrevmats.2016.103Google Scholar3Lithium battery chemistries enabled by solid-state electrolytesManthiram, Arumugam; Yu, Xingwen; Wang, ShaofeiNature Reviews Materials (2017), 2 (3), 16103CODEN: NRMADL; ISSN:2058-8437. (Nature Publishing Group)Solid-state electrolytes are attracting increasing interest for electrochem. energy storage technologies. In this Review, we provide a background overview and discuss the state of the art, ion-transport mechanisms and fundamental properties of solid-state electrolyte materials of interest for energy storage applications. We focus on recent advances in various classes of battery chemistries and systems that are enabled by solid electrolytes, including all-solid-state lithium-ion batteries and emerging solid-electrolyte lithium batteries that feature cathodes with liq. or gaseous active materials (for example, lithium-air, lithium-sulfur and lithium-bromine systems). A low-cost, safe, aq. electrochem. energy storage concept with a 'mediator-ion' solid electrolyte is also discussed. Advanced battery systems based on solid electrolytes would revitalize the rechargeable battery field because of their safety, excellent stability, long cycle lives and low cost. However, great effort will be needed to implement solid-electrolyte batteries as viable energy storage systems. In this context, we discuss the main issues that must be addressed, such as achieving acceptable ionic cond., electrochem. stability and mech. properties of the solid electrolytes, as well as a compatible electrolyte/electrode interface.
- 4Wang, Y.; Richards, W. D.; Ong, S. P.; Miara, L. J.; Kim, J. C.; Mo, Y.; Ceder, G. Design Principles for Solid-State Lithium Superionic Conductors. Nat. Mater. 2015, 14, 1026– 1031, DOI: 10.1038/nmat4369Google Scholar4Design principles for solid-state lithium superionic conductorsWang, Yan; Richards, William Davidson; Ong, Shyue Ping; Miara, Lincoln J.; Kim, Jae Chul; Mo, Yifei; Ceder, GerbrandNature Materials (2015), 14 (10), 1026-1031CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)Lithium solid electrolytes can potentially address two key limitations of the org. electrolytes used in today's lithium-ion batteries, namely, their flammability and limited electrochem. stability. However, achieving a Li+ cond. in the solid state comparable to existing liq. electrolytes (>1 mS cm-1) is particularly challenging. In this work, we reveal a fundamental relationship between anion packing and ionic transport in fast Li-conducting materials and expose the desirable structural attributes of good Li-ion conductors. We find that an underlying body-centered cubic-like anion framework, which allows direct Li hops between adjacent tetrahedral sites, is most desirable for achieving high ionic cond., and that indeed this anion arrangement is present in several known fast Li-conducting materials and other fast ion conductors. These findings provide important insight towards the understanding of ionic transport in Li-ion conductors and serve as design principles for future discovery and design of improved electrolytes for Li-ion batteries.
- 5Kamaya, N.; Homma, K.; Yamakawa, Y.; Hirayama, M.; Kanno, R.; Yonemura, M.; Kamiyama, T.; Kato, Y.; Hama, S.; Kawamoto, K.; Mitsui, A. A Lithium Superionic Conductor. Nat. Mater. 2011, 10, 682– 686, DOI: 10.1038/nmat3066Google Scholar5A lithium superionic conductorKamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro; Hirayama, Masaaki; Kanno, Ryoji; Yonemura, Masao; Kamiyama, Takashi; Kato, Yuki; Hama, Shigenori; Kawamoto, Koji; Mitsui, AkioNature Materials (2011), 10 (9), 682-686CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)Batteries are a key technol. in modern society. They are used to power elec. and hybrid elec. vehicles and to store wind and solar energy in smart grids. Electrochem. devices with high energy and power densities can currently be powered only by batteries with org. liq. electrolytes. However, such batteries require relatively stringent safety precautions, making large-scale systems complicated and expensive. The application of solid electrolytes is currently limited because they attain practically useful conductivities (10-2 S/cm) only at 50-80°, which is one order of magnitude lower than those of org. liq. electrolytes. Here, the authors report a Li superionic conductor, Li10GeP2S12 that has a new 3-dimensional framework structure. It exhibits an extremely high Li ionic cond. of 12 mS/cm at room temp. This represents the highest cond. achieved in a solid electrolyte, exceeding even those of liq. org. electrolytes. This new solid-state battery electrolyte has many advantages in terms of device fabrication (facile shaping, patterning and integration), stability (non-volatile), safety (non-explosive) and excellent electrochem. properties (high cond. and wide potential window).
- 6Kato, Y.; Hori, S.; Saito, T.; Suzuki, K.; Hirayama, M.; Mitsui, A.; Yonemura, M.; Iba, H.; Kanno, R. High-Power All-Solid-State Batteries Using Sulfide Superionic Conductors. Nat. Energy 2016, 1, 16030, DOI: 10.1038/nenergy.2016.30Google Scholar6High-power all-solid-state batteries using sulfide superionic conductorsKato, Yuki; Hori, Satoshi; Saito, Toshiya; Suzuki, Kota; Hirayama, Masaaki; Mitsui, Akio; Yonemura, Masao; Iba, Hideki; Kanno, RyojiNature Energy (2016), 1 (4), 16030CODEN: NEANFD; ISSN:2058-7546. (Nature Publishing Group)Compared with Li-ion batteries with liq. electrolytes, all-solid-state batteries offer an attractive option owing to their potential in improving the safety and achieving both high power and high energy densities. Despite extensive research efforts, the development of all-solid-state batteries still falls short of expectation largely because of the lack of suitable candidate materials for the electrolyte required for practical applications. Here the authors report Li superionic conductors with an exceptionally high cond. (25 mS cm-1 for Li9.54Si1.74P1.44S11.7Cl0.3), as well as high stability ( ∼0 V vs. Li metal for Li9.6P3S12). A fabricated all-solid-state cell based on this Li conductor has very small internal resistance, esp. at 100 oC. The cell possesses high specific power that is superior to that of conventional cells with liq. electrolytes. Stable cycling with a high c.d. of 18 C (charging/discharging in just 3 min; where C is the C-rate) is also demonstrated.
- 7Murugan, R.; Thangadurai, V.; Weppner, W. Fast Lithium Ion Conduction in Garnet-Type Li7La3Zr2O12. Angew. Chem., Int. Ed. 2007, 46, 7778– 7781, DOI: 10.1002/anie.200701144Google Scholar7Fast lithium ion conduction in garnet-type Li7La3Zr2O12Murugan, Ramaswamy; Thangadurai, Venkataraman; Weppner, WernerAngewandte Chemie, International Edition (2007), 46 (41), 7778-7781CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)Low activation energy and fast Li ion conduction were obsd. for the new compd., Li7La3Zr2O12. Relative to previously reported Li garnets, this solid electrolyte shows a larger cubic lattice const., higher Li ion concn., lower degree of chem. interaction between the Li+ and the other lattice constituents, and higher densification.
- 8Liu, Z.; Fu, W.; Payzant, E. A.; Yu, X.; Wu, Z.; Dudney, N. J.; Kiggans, J.; Hong, K.; Rondinone, A. J.; Liang, C. Anomalous High Ionic Conductivity of Nanoporous β-Li3PS4. J. Am. Chem. Soc. 2013, 135, 975– 978, DOI: 10.1021/ja3110895Google Scholar8Anomalous High Ionic Conductivity of Nanoporous β-Li3PS4Liu, Zengcai; Fu, Wujun; Payzant, E. Andrew; Yu, Xiang; Wu, Zili; Dudney, Nancy J.; Kiggans, Jim; Hong, Kunlun; Rondinone, Adam J.; Liang, ChengduJournal of the American Chemical Society (2013), 135 (3), 975-978CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Lithium-ion-conducting solid electrolytes hold promise for enabling high-energy battery chemistries and circumventing safety issues of conventional lithium batteries. Achieving the combination of high ionic cond. and a broad electrochem. window in solid electrolytes is a grand challenge for the synthesis of battery materials. Herein we show an enhancement of the room-temp. lithium-ion cond. by 3 orders of magnitude through the creation of nanostructured Li3PS4. This material has a wide electrochem. window (5 V) and superior chem. stability against lithium metal. The nanoporous structure of Li3PS4 reconciles two vital effects that enhance the ionic cond.: (a) the redn. of the dimensions to a nanometer-sized framework stabilizes the high-conduction β phase that occurs at elevated temps., and (b) the high surface-to-bulk ratio of nanoporous β-Li3PS4 promotes surface conduction. Manipulating the ionic cond. of solid electrolytes has far-reaching implications for materials design and synthesis in a broad range of applications, including batteries, fuel cells, sensors, photovoltaic systems, and so forth.
- 9Du, M.; Liao, K.; Lu, Q.; Shao, Z. Recent Advances in the Interface Engineering of Solid-State Li-Ion Batteries with Artificial Buffer Layers: Challenges, Materials, Construction, and Characterization. Energy Environ. Sci. 2019, 12, 1780– 1804, DOI: 10.1039/C9EE00515CGoogle Scholar9Recent advances in the interface engineering of solid-state Li-ion batteries with artificial buffer layers: challenges, materials, construction, and characterizationDu, Mingjie; Liao, Kaiming; Lu, Qian; Shao, ZongpingEnergy & Environmental Science (2019), 12 (6), 1780-1804CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)A review. Although solid-state Li-ion batteries (SSBs) provide opportunities to simplify safety measures (e.g., sophisticated thermal management systems, overpressure vents, charge interruption devices) currently used in conventional Li-ion batteries (LIBs) with flammable org. liq. electrolytes, the poor interface compatibility (both phys. and chem.) between the electrode materials and solid electrolyte strongly hinders the practical application of SSBs. The fabrication of artificial buffer layers (ABLs) was therefore proposed, and it has been an effective approach for overcoming the interface issues of SSBs. In this review paper, we provide a comprehensive summary of recent progress in interface engineering and advanced techniques for characterization of such interfaces in SSBs. First, the crit. issues and challenges facing SSBs assocd. with the stability of the cathode/solid electrolyte and anode/solid electrolyte interfaces are discussed. The latest research approaches and synthetic strategies to improve the performance of SSBs that rely on interface engineering with ABLs are extensively reviewed. The characterization strategies for in situ and ex situ interfacial observation and anal. are comprehensively summarized. Finally, the crit. issues assocd. with electrode-electrolyte interfaces are emphasized, and perspectives regarding the development of high-quality buffer layers are presented.
- 10Auvergniot, J.; Cassel, A.; Ledeuil, J.-B.; Viallet, V.; Seznec, V.; Dedryvère, R. Interface Stability of Argyrodite Li6PS5Cl toward LiCoO2, LiNi1/3Co1/3Mn1/3O2, and LiMn2O4 in Bulk All-Solid-State Batteries. Chem. Mater. 2017, 29, 3883– 3890, DOI: 10.1021/acs.chemmater.6b04990Google Scholar10Interface Stability of Argyrodite Li6PS5Cl toward LiCoO2, LiNi1/3Co1/3Mn1/3O2, and LiMn2O4 in Bulk All-Solid-State BatteriesAuvergniot, Jeremie; Cassel, Alice; Ledeuil, Jean-Bernard; Viallet, Virginie; Seznec, Vincent; Dedryvere, RemiChemistry of Materials (2017), 29 (9), 3883-3890CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Argyrodite Li6PS5Cl is a good candidate for being a solid electrolyte for bulk all-solid-state Li-ion batteries because of its high ionic cond. and its good processability. However, the interface stability of sulfide-based electrolytes toward active materials (neg. or pos. electrodes) is known to be lower than that of oxide-based electrolytes. In this work, we investigate the interface stability of argyrodite toward several pos. electrode materials: LiCoO2, LiNi1/3Co1/3Mn1/3O2, and LiMn2O4. All-solid-state half-cells were cycled, and the interface mechanisms were characterized by Auger electron spectroscopy and XPS. We show that Li6PS5Cl is oxidized into elemental sulfur, lithium polysulfides, P2Sx (x ≥ 5), phosphates, and LiCl at the interface with the pos. electrode active materials. In spite of this interface reactivity, good capacity retention was obsd. over 300 cycles. Li6PS5Cl shows some reversible electrochem. activity (redox processes) that might contribute to the reversible capacity of the battery.
- 11Dai, J.; Yang, C.; Wang, C.; Pastel, G.; Hu, L. Interface Engineering for Garnet-Based Solid-State Lithium-Metal Batteries: Materials, Structures, and Characterization. Adv. Mater. 2018, 30, 1802068, DOI: 10.1002/adma.201802068Google ScholarThere is no corresponding record for this reference.
- 12Han, X.; Gong, Y.; Fu, K.; He, X.; Hitz, G. T.; Dai, J.; Pearse, A.; Liu, B.; Wang, H.; Rubloff, G.; Mo, Y.; Thangadurai, V.; Wachsman, E. D.; Hu, L. Negating Interfacial Impedance in Garnet-Based Solid-State Li Metal Batteries. Nat. Mater. 2017, 16, 572– 579, DOI: 10.1038/nmat4821Google Scholar12Negating interfacial impedance in garnet-based solid-state Li metal batteriesHan, Xiaogang; Gong, Yunhui; Fu, Kun; He, Xingfeng; Hitz, Gregory T.; Dai, Jiaqi; Pearse, Alex; Liu, Boyang; Wang, Howard; Rubloff, Gary; Mo, Yifei; Thangadurai, Venkataraman; Wachsman, Eric D.; Hu, LiangbingNature Materials (2017), 16 (5), 572-579CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)Garnet-type solid-state electrolytes have attracted extensive attention due to their high ionic cond., approaching 1 mS cm-1, excellent environmental stability, and wide electrochem. stability window, from lithium metal to ∼6 V. However, to date, there has been little success in the development of high-performance solid-state batteries using these exceptional materials, the major challenge being the high solid-solid interfacial impedance between the garnet electrolyte and electrode materials. In this work, we effectively address the large interfacial impedance between a lithium metal anode and the garnet electrolyte using ultrathin aluminum oxide (Al2O3) by at. layer deposition. Li7La2.75Ca0.25Zr1.75Nb0.25O12 (LLCZN) is the garnet compn. of choice in this work due to its reduced sintering temp. and increased lithium ion cond. A significant decrease of interfacial impedance, from 1,710 Ω cm2 to 1 Ω cm2, was obsd. at room temp., effectively negating the lithium metal/garnet interfacial impedance. Exptl. and computational results reveal that the oxide coating enables wetting of metallic lithium in contact with the garnet electrolyte surface and the lithiated-alumina interface allows effective lithium ion transport between the lithium metal anode and garnet electrolyte. We also demonstrate a working cell with a lithium metal anode, garnet electrolyte and a high-voltage cathode by applying the newly developed interface chem.
- 13Ahmad, Z.; Viswanathan, V. Stability of Electrodeposition at Solid-Solid Interfaces and Implications for Metal Anodes. Phys. Rev. Lett. 2017, 119, 056003, DOI: 10.1103/PhysRevLett.119.056003Google Scholar13Stability of electrodeposition at solid-solid interfaces and implications for metal anodesAhmad, Zeeshan; Viswanathan, VenkatasubramanianPhysical Review Letters (2017), 119 (5), 056003/1-056003/6CODEN: PRLTAO; ISSN:1079-7114. (American Physical Society)We generalize the conditions for stable electrodeposition at isotropic solid-solid interfaces using a kinetic model which incorporates the effects of stresses and surface tension at the interface. We develop a stability diagram that shows two regimes of stability: a previously known pressure-driven mechanism and a new d.-driven stability mechanism that is governed by the relative d. of metal in the two phases. We show that inorg. solids and solid polymers generally do not lead to stable electrodeposition, and provide design guidelines for achieving stable electrodeposition.
- 14Gao, B.; Jalem, R.; Ma, Y.; Tateyama, Y. Li+ Transport Mechanism at the Heterogeneous Cathode/Solid Electrolyte Interface in an All-Solid-State Battery via the First-Principles Structure Prediction Scheme. Chem. Mater. 2020, 32, 85– 96, DOI: 10.1021/acs.chemmater.9b02311Google Scholar14Li+ Transport Mechanism at the Heterogeneous Cathode/Solid Electrolyte Interface in an All-Solid-State Battery via the First-Principles Structure Prediction SchemeGao, Bo; Jalem, Randy; Ma, Yanming; Tateyama, YoshitakaChemistry of Materials (2020), 32 (1), 85-96CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)High interfacial resistance between a cathode and solid electrolyte (SE) has been a long-standing problem for all-solid-state batteries (ASSBs). Though thermodn. approaches suggested possible phase transformations at the interfaces, direct analyses of the ionic and electronic states at the solid/solid interfaces are still crucial. Here, newly constructed scheme is used for predicting heterogeneous interface structures via the swarm-intelligence-based crystal structure anal. by particle swarm optimization method, combined with d. functional theory calcns., and systematically investigated the mechanism of Li-ion (Li+) transport at the interface in LiCoO2 cathode/β-Li3PS4 SE, a representative ASSB system. The sampled favorable interface structures indicate that the interfacial reaction layer is formed with both mixing of Co and P cations and mixing of O and S anions. The calcd. site-dependent Li chem. potentials μLi(r) and potential energy surfaces for Li+ migration across the interfaces reveal that interfacial Li+ sites with higher μLi(r) values cause dynamic Li+ depletion with the interfacial electron transfer in the initial stage of charging. The Li+-depleted space can allow oxidative decompn. of SE materials. These pieces of evidence theor. confirm the primary origin of the obsd. interfacial resistance in ASSBs and the mechanism of the resistance decrease obsd. with oxide buffer layers (e.g., LiNbO3) and oxide SE. The present study also provides a perspective for the structure sampling of disordered heterogeneous solid/solid interfaces on the at. scale.
- 15Takada, K. Progress and Prospective of Solid-State Lithium Batteries. Acta Mater. 2013, 61, 759– 770, DOI: 10.1016/j.actamat.2012.10.034Google Scholar15Progress and prospective of solid-state lithium batteriesTakada, KazunoriActa Materialia (2013), 61 (3), 759-770CODEN: ACMAFD; ISSN:1359-6454. (Elsevier Ltd.)A review. The development of lithium-ion batteries has energized studies of solid-state batteries, because the non-flammability of their solid electrolytes offers a fundamental soln. to safety concerns. Since poor ionic conduction in solid electrolytes is a major drawback in solid-state batteries, such studies were focused on the enhancement of ionic cond. The studies have identified some high performance solid electrolytes; however, some disadvantages have remained hidden until their use in batteries. This paper reviews the development of solid electrolytes and their application to solid-state lithium batteries.
- 16Takada, K.; Ohta, N.; Zhang, L.; Fukuda, K.; Sakaguchi, I.; Ma, R.; Osada, M.; Sasaki, T. Interfacial Modification for High-Power Solid-State Lithium Batteries. Solid State Ionics 2008, 179, 1333– 1337, DOI: 10.1016/j.ssi.2008.02.017Google Scholar16Interfacial modification for high-power solid-state lithium batteriesTakada, Kazunori; Ohta, Narumi; Zhang, Lianqi; Fukuda, Katsutoshi; Sakaguchi, Isao; Ma, Renzhi; Osada, Minoru; Sasaki, TakayoshiSolid State Ionics (2008), 179 (27-32), 1333-1337CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)Interfaces between LiCoO2 and sulfide solid electrolytes were modified in order to enhance the high-rate capability of solid-state lithium batteries. Thin films of oxide solid electrolytes, Li4Ti5O12, LiNbO3, and LiTaO3, were interposed at the interfaces as buffer layers. Changes in the high-rate performance upon heat treatment revealed that the buffer layer should be formed at low temp. to avoid thermal diffusion of the elements. Buffer layers of LiNbO3 and LiTaO3 can be formed at low temp. for the interfacial modification, because they show high ionic conduction in their amorphous states, and so are more effective than Li4Ti5O12 for high-power densities.
- 17Haruyama, J.; Sodeyama, K.; Han, L.; Takada, K.; Tateyama, Y. Space–Charge Layer Effect at Interface between Oxide Cathode and Sulfide Electrolyte in All-Solid-State Lithium-Ion Battery. Chem. Mater. 2014, 26, 4248– 4255, DOI: 10.1021/cm5016959Google Scholar17Space-Charge Layer Effect at Interface between Oxide Cathode and Sulfide Electrolyte in All-Solid-State Lithium-Ion BatteryHaruyama, Jun; Sodeyama, Keitaro; Han, Liyuan; Takada, Kazunori; Tateyama, YoshitakaChemistry of Materials (2014), 26 (14), 4248-4255CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)The authors theor. elucidated the characteristics of the space-charge layer (SCL) at interfaces between oxide cathode and sulfide electrolyte in all-solid-state Li-ion batteries (ASS-LIBs) and the effect of the buffer layer interposition, for the 1st time, via the calcns. with d. functional theory (DFT) + U framework. As a most representative system, the authors examd. the interfaces between LiCoO2 cathode and β-Li3PS4 solid electrolyte (LCO/LPS), and the LiCoO2/LiNbO3/β-Li3PS4 (LCO/LNO/LPS) interfaces with the LiNbO3 buffer layers. The DFT+U calcns., coupling with a systematic procedure for interface matching, showed the stable structures and the electronic states of the interfaces. The LCO/LPS interface has attractive Li adsorption sites and rather disordered structure, whereas the interposition of the LNO buffer layers forms smooth interfaces without Li adsorption sites for both LCO and LPS sides. The calcd. energies of the Li-vacancy formation and the Li migration reveal that subsurface Li in the LPS side can begin to transfer at the under-voltage condition in the LCO/LPS interface, which suggests the SCL growth at the beginning of charging, leading to the interfacial resistance. The LNO interposition suppresses this growth of SCL and provides smooth Li transport paths free from the possible bottlenecks. These aspects on the at. scale will give a useful perspective for the further improvement of the ASS-LIB performance.
- 18Sakuda, A.; Hayashi, A.; Tatsumisago, M. Interfacial Observation between LiCoO2 Electrode and Li2S–P2S5 Solid Electrolytes of All-Solid-State Lithium Secondary Batteries Using Transmission Electron Microscopy. Chem. Mater. 2010, 22, 949– 956, DOI: 10.1021/cm901819cGoogle Scholar18Interfacial Observation between LiCoO2 Electrode and Li2S-P2S5 Solid Electrolytes of All-Solid-State Lithium Secondary Batteries using Transmission Electron MicroscopySakuda, Atsushi; Hayashi, Akitoshi; Tatsumisago, MasahiroChemistry of Materials (2010), 22 (3), 949-956CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)In all-solid-state lithium secondary batteries, both the electrode and electrolyte materials are solid. The electrode and solid electrolyte interface structure and morphol. affect a battery electrochem. performance. Observation of the interface between LiCoO2 cathode and highly lithium-ion-conducting Li2S-P2S5 solid electrolyte was conducted using transmission electron microscopy. An interfacial layer was formed at the interface between LiCoO2 electrode and Li2S-P2S5 solid electrolyte after the battery initial charge. Furthermore, mutual diffusions of Co, P, and S at the interface between LiCoO2 and Li2S-P2S5 were obsd. The mutual diffusion and the formation of the interfacial layer were suppressed using LiCoO2 particles coated with Li2SiO3 thin film. Results showed that all-solid-state batteries using Li2SiO3-coated LiCoO2 had better electrochem. performance than those using non-coated LiCoO2. The all-solid-state batteries functioned at -30°. Moreover, the all-solid-state battery using Li2SiO3-coated LiCoO2 was charged and discharged under a high c.d. of 40 mA/cm2 at 100°.
- 19Koerver, R.; Zhang, W.; de Biasi, L.; Schweidler, S.; Kondrakov, A. O.; Kolling, S.; Brezesinski, T.; Hartmann, P.; Zeier, G. W.; Janek, J. Chemo-Mechanical Expansion of Lithium Electrode Materials—on the Route to Mechanically Optimized All-Solid-State Batteries. Energy Environ. Sci. 2018, 11, 2142– 2158, DOI: 10.1039/C8EE00907DGoogle Scholar19Chemo-mechanical expansion of lithium electrode materials - on the route to mechanically optimized all-solid-state batteriesKoerver, Raimund; Zhang, Wenbo; de Biasi, Lea; Schweidler, Simon; Kondrakov, Aleksandr O.; Kolling, Stefan; Brezesinski, Torsten; Hartmann, Pascal; Zeier, Wolfgang G.; Janek, JuergenEnergy & Environmental Science (2018), 11 (8), 2142-2158CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)Charge and discharge of lithium ion battery electrodes is accompanied by severe vol. changes. In a confined space, the vol. cannot expand, leading to significant pressures induced by local microstructural changes within the battery. While vol. changes appear to be less crit. in batteries with liq. electrolytes, they will be more crit. in the case of lithium ion batteries with solid electrolytes and they will be even more crit. and detrimental in the case of all-solid-state batteries with a lithium metal electrode. In this work we first summarize, compare, and analyze the vol. changes occurring in state of the art electrode materials, based on crystallog. studies. A quant. anal. follows that is based on the evaluation of the partial molar volume of lithium as a function of the degree of lithiation for different electrode materials. Second, the reaction vols. of operating full cells ("charge/discharge vols.") are exptl. detd. from pressure-dependent open-circuit voltage measurements. The resulting changes in the open-circuit voltage are in the order of 1 mV/100 MPa, are well measurable, and agree with changes obsd. in the crystallog. data. Third, the pressure changes within solid-state batteries are approximated under the assumption of incompressibility, i.e. for const. vol. of the cell casing, and are compared to exptl. data obtained from model-type full cells. In addn. to the understanding of the occurring vol. changes of electrode materials and resulting pressure changes in solid-state batteries, we propose "mech." blending of electrode materials to achieve better cycling performance when aiming at "zero-strain" electrodes.
- 20Koerver, R.; Aygün, I.; Leichtweiß, T.; Dietrich, C.; Zhang, W.; Binder, J. O.; Hartmann, P.; Zeier, W. G.; Janek, J. Capacity Fade in Solid-State Batteries: Interphase Formation and Chemomechanical Processes in Nickel-Rich Layered Oxide Cathodes and Lithium Thiophosphate Solid Electrolytes. Chem. Mater. 2017, 29, 5574– 5582, DOI: 10.1021/acs.chemmater.7b00931Google Scholar20Capacity Fade in Solid-State Batteries: Interphase Formation and Chemomechanical Processes in Nickel-Rich Layered Oxide Cathodes and Lithium Thiophosphate Solid ElectrolytesKoerver, Raimund; Ayguen, Isabel; Leichtweiss, Thomas; Dietrich, Christian; Zhang, Wenbo; Binder, Jan O.; Hartmann, Pascal; Zeier, Wolfgang G.; Janek, JuergenChemistry of Materials (2017), 29 (13), 5574-5582CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)All-solid-state lithium ion batteries may become long-term, stable, high-performance energy storage systems for the next generation of elec. vehicles and consumer electronics, depending on the compatibility of electrode materials and suitable solid electrolytes. Nickel-rich layered oxides are nowadays the benchmark cathode materials for conventional lithium ion batteries because of their high storage capacity and the resulting high energy d., and their use in solid-state systems is the next necessary step. In this study, we present the successful implementation of a Li[Ni,Co,Mn]O2 material with high nickel content (LiNi0.8Co0.1Mn0.1O2, NCM-811) in a bulk-type solid-state battery with β-Li3PS4 as a sulfide-based solid electrolyte. We investigate the interface behavior at the cathode and demonstrate the important role of the interface between the active materials and the solid electrolyte for the battery performance. A passivating cathode/electrolyte interphase layer forms upon charging and leads to an irreversible first cycle capacity loss, corresponding to a decompn. of the sulfide electrolyte. In situ electrochem. impedance spectroscopy and X-ray photoemission spectroscopy are used to monitor this formation. We demonstrate that most of the interphase formation takes place in the first cycle, when charging to potentials above 3.8 V vs Li+/Li. The resulting overvoltage of the passivating layer is a detrimental factor for capacity retention. In addn. to the interfacial decompn., the chemomech. contraction of the active material upon delithiation causes contact loss between the solid electrolyte and active material particles, further increasing the interfacial resistance and capacity loss. These results highlight the crit. role of (electro-)chemo-mech. effects in solid-state batteries.
- 21Swift, M. W.; Qi, Y. First-Principles Prediction of Potentials and Space-Charge Layers in All-Solid-State Batteries. Phys. Rev. Lett. 2019, 122, 167701, DOI: 10.1103/PhysRevLett.122.167701Google Scholar21First-Principles Prediction of Potentials and Space-Charge Layers in All-Solid-State BatteriesSwift, Michael W.; Qi, YuePhysical Review Letters (2019), 122 (16), 167701pp.CODEN: PRLTAO; ISSN:1079-7114. (American Physical Society)As all-solid-state batteries (SSBs) develop as an alternative to traditional cells, a thorough theor. understanding of driving forces behind battery operation is needed. We present a fully first-principles-informed model of potential profiles in SSBs and apply the model to the Li/LiPON/LixCoO2 system. The model predicts interfacial potential drops driven by both electron transfer and Li+ space-charge layers that vary with the SSB's state of charge. The results suggest a lower electronic ionization potential in the solid electrolyte favors Li+ transport, leading to higher discharge power.
- 22Nomura, Y.; Yamamoto, K.; Hirayama, T.; Ouchi, S.; Igaki, E.; Saitoh, K. Direct Observation of a Li-Ionic Space-Charge Layer Formed at an Electrode/Solid-Electrolyte Interface. Angew. Chem. 2019, 131, 5346– 5350, DOI: 10.1002/ange.201814669Google ScholarThere is no corresponding record for this reference.
- 23Tian, H.-K.; Qi, Y. Simulation of the Effect of Contact Area Loss in All-Solid-State Li-Ion Batteries. J. Electrochem. Soc. 2017, 164, E3512– E3521, DOI: 10.1149/2.0481711jesGoogle Scholar23Simulation of the Effect of Contact Area Loss in All-Solid-State Li-Ion BatteriesTian, Hong-Kang; Qi, YueJournal of the Electrochemical Society (2017), 164 (11), E3512-E3521CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)Maintaining the phys. contact between the solid electrolyte and the electrode is important to improve the performance of all-solid-state batteries. Imperfect contact can be formed during cell fabrication and will be worsened due to cycling, resulting in degrdn. of the battery performance. In this paper, the effect of imperfect contact area was incorporated into a 1-D Newman battery model by assuming the current and Li concn. will be localized at the contacted area. Const. current discharging processes at different rates and contact areas were simulated for a film-type Li/LiPON/LiCoO2 all-solid-state Li-ion battery. The capacity drop was correlated with the contact area loss. It was found at lower cutoff voltage, the correlation is almost linear with a slope of 1; while at a higher cutoff voltage, the dropping rate is slower. To establish the relationship between the applied pressure and the contact area, Persson's contact mechanics theory was applied, as it uses self-affined surfaces to simplify the multi-length scale contacts in all-solid-state batteries. The contact area and pressure were computed for both film-type and bulk-type all-solid-state Li-ion batteries. The model is then used to suggest how much pressures should be applied to recover the capacity drop due to contact area loss.
- 24Aguesse, F.; Manalastas, W.; Buannic, L.; Lopez del Amo, J. M.; Singh, G.; Llordés, A.; Kilner, J. Investigating the Dendritic Growth during Full Cell Cycling of Garnet Electrolyte in Direct Contact with Li Metal. ACS Appl. Mater. Interfaces 2017, 9, 3808– 3816, DOI: 10.1021/acsami.6b13925Google Scholar24Investigating the Dendritic Growth during Full Cell Cycling of Garnet Electrolyte in Direct Contact with Li MetalAguesse, Frederic; Manalastas, William; Buannic, Lucienne; Lopez del Amo, Juan Miguel; Singh, Gurpreet; Llordes, Anna; Kilner, JohnACS Applied Materials & Interfaces (2017), 9 (4), 3808-3816CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)All-solid-state batteries including a garnet ceramic as electrolyte are potential candidates to replace the currently used Li-ion technol., as they offer safer operation and higher energy storage performances. However, the development of ceramic electrolyte batteries faces several challenges at the electrode/electrolyte interfaces, which need to withstand high current densities to enable competing C-rates. The authors study the limits of the anode/electrolyte interface in a full cell that includes a Li-metal anode, LiFePO4 cathode, and garnet ceramic electrolyte. The addn. of a liq. interfacial layer between the cathode and the ceramic electrolyte is a prerequisite to achieve low interfacial resistance and to enable full use of the active material contained in the porous electrode. Reproducible and const. discharge capacities are extd. from the cathode active material during the 1st 20 cycles, revealing high efficiency of the garnet as electrolyte and the interfaces, but prolonged cycling leads to abrupt cell failure. By using a combination of structural and chem. characterization techniques, such as SEM and solid-state NMR, as well as electrochem. and impedance spectroscopy, a sudden impedance drop occurs in the cell due to the formation of metallic Li and its propagation within the ceramic electrolyte. This degrdn. process is originated at the interface between the Li-metal anode and the ceramic electrolyte layer and leads to electromech. failure and cell short-circuit. Improvement of the performances is obsd. when cycling the full cell at 55°, as the Li-metal softening favors the interfacial contact. Various degrdn. mechanisms probably explain this behavior.
- 25Krauskopf, T.; Hartmann, H.; Zeier, W. G.; Janek, J. Toward a Fundamental Understanding of the Lithium Metal Anode in Solid-State Batteries—An Electrochemo-Mechanical Study on the Garnet-Type Solid Electrolyte Li6.25Al0.25La3Zr2O12. ACS Appl. Mater. Interfaces 2019, 11, 14463– 14477, DOI: 10.1021/acsami.9b02537Google Scholar25Toward a Fundamental Understanding of the Lithium Metal Anode in Solid-State Batteries-An Electrochemo-Mechanical Study on the Garnet-Type Solid Electrolyte Li6.25Al0.25La3Zr2O12Krauskopf, Thorben; Hartmann, Hannah; Zeier, Wolfgang G.; Janek, JuergenACS Applied Materials & Interfaces (2019), 11 (15), 14463-14477CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)For the development of next-generation lithium batteries, major research effort is made to enable a reversible lithium metal anode by the use of solid electrolytes. However, the fundamentals of the solid-solid interface and esp. the processes that take place under current load are still not well characterized. By measuring pressure-dependent electrode kinetics, we explore the electrochemo-mech. behavior of the lithium metal anode on the garnet electrolyte Li6.25Al0.25La3Zr2O12. Because of the stability against redn. in contact with the lithium metal, this serves as an optimal model system for kinetic studies without electrolyte degrdn. We show that the interfacial resistance becomes negligibly small and converges to practically 0 Ω·cm2 at high external pressures of several 100 MPa. To the best of our knowledge, this is the smallest reported interfacial resistance in the literature without the need for any interlayer. We interpret this observation by the concept of constriction resistance and show that the contact geometry in combination with the ionic transport in the solid electrolyte dominates the interfacial contributions for a clean interface in equil. Furthermore, we show that-under anodic operating conditions-the vacancy diffusion limitation in the lithium metal restricts the rate capability of the lithium metal anode because of contact loss caused by vacancy accumulation and the resulting pore formation near the interface. Results of a kinetic model show that the interface remains morphol. stable only when the anodic load does not exceed a crit. value of approx. 100 μA·cm-2, which is not high enough for practical cell setups employing a planar geometry. We highlight that future research on lithium metal anodes on solid electrolytes needs to focus on the transport within and the morphol. instability of the metal electrode. Overall, the results help to develop a deeper understanding of the lithium metal anode on solid electrolytes, and the major conclusions are not limited to the Li|Li6.25Al0.25La3Zr2O12 interface.
- 26Zhang, W.; Richter, F. H.; Culver, S. P.; Leichtweiss, T.; Lozano, J. G.; Dietrich, C.; Bruce, P. G.; Zeier, W. G.; Janek, J. Degradation Mechanisms at the Li10GeP2S12/LiCoO2 Cathode Interface in an All-Solid-State Lithium-Ion Battery. ACS Appl. Mater. Interfaces 2018, 10, 22226– 22236, DOI: 10.1021/acsami.8b05132Google Scholar26Degradation mechanisms at the Li10GeP2S12/LiCoO2 cathode interface in an all-solid-state lithium-ion batteryZhang, Wenbo; Richter, Felix H.; Culver, Sean P.; Leichtweiss, Thomas; Lozano, Juan G.; Dietrich, Christian; Bruce, Peter G.; Zeier, Wolfgang G.; Janek, JuergenACS Applied Materials & Interfaces (2018), 10 (26), 22226-22236CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)All-solid-state batteries (ASSBs) show great potential for providing high power and energy densities with enhanced battery safety. While new solid electrolytes (SEs) have been developed with high enough ionic conductivities, SSBs with long operational life are still rarely reported. Therefore, on the way to high-performance and long-life ASSBs, a better understanding of the complex degrdn. mechanisms, occurring at the electrode/electrolyte interfaces is pivotal. While the lithium metal/solid electrolyte interface is receiving considerable attention due to the quest for high energy d., the interface between the active material and solid electrolyte particles within the composite cathode is arguably the most difficult to solve and study. In this work, multiple characterization methods are combined to better understand the processes that occur at the LiCoO2 cathode and the Li10GeP2S12 solid electrolyte interface. Indium and Li4Ti5O12 are used as anode materials to avoid the instability problems assocd. with Li-metal anodes. Capacity fading and increased impedances are obsd. during long-term cycling. Postmortem anal. with scanning transmission electron microscopy, electron energy loss spectroscopy, x-ray diffraction, and XPS show that electrochem. driven mech. failure and degrdn. at the cathode/solid electrolyte interface contribute to the increase in internal resistance and the resulting capacity fading. These results suggest that the development of electrochem. more stable SEs and the engineering of cathode/SE interfaces are crucial for achieving reliable SSB performance.
- 27Richards, W. D.; Miara, L. J.; Wang, Y.; Kim, J. C.; Ceder, G. Interface Stability in Solid-State Batteries. Chem. Mater. 2016, 28, 266– 273, DOI: 10.1021/acs.chemmater.5b04082Google Scholar27Interface Stability in Solid-State BatteriesRichards, William D.; Miara, Lincoln J.; Wang, Yan; Kim, Jae Chul; Ceder, GerbrandChemistry of Materials (2016), 28 (1), 266-273CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Development of high cond. solid-state electrolytes for lithium ion batteries has proceeded rapidly in recent years, but incorporating these new materials into high-performing batteries has proven difficult. Interfacial resistance is now the limiting factor in many systems, but the exact mechanisms of this resistance have not been fully explained - in part because exptl. evaluation of the interface can be very difficult. In this work, we develop a computational methodol. to examine the thermodn. of formation of resistive interfacial phases. The predicted interfacial phase formation is well correlated with exptl. interfacial observations and battery performance. We calc. that thiophosphate electrolytes have esp. high reactivity with high voltage cathodes and a narrow electrochem. stability window. We also find that a no. of known electrolytes are not inherently stable but react in situ with the electrode to form passivating but ionically conducting barrier layers. As a ref. for experimentalists, we tabulate the stability and expected decompn. products for a wide range of electrolyte, coating, and electrode materials including a no. of high-performing combinations that have not yet been attempted exptl.
- 28Han, F.; Zhu, Y.; He, X.; Mo, Y.; Wang, C. Electrochemical Stability of Li10GeP2S12 and Li7La3Zr2O12 Solid Electrolytes. Adv. Energy Mater. 2016, 6, 1501590, DOI: 10.1002/aenm.201501590Google ScholarThere is no corresponding record for this reference.
- 29Gao, B.; Jalem, R.; Tateyama, Y. Surface-Dependent Stability of the Interface between Garnet Li7La3Zr2O12 and the Li Metal in the All-Solid-State Battery from First-Principles Calculations. ACS Appl. Mater. Interfaces 2020, 12, 16350– 16358, DOI: 10.1021/acsami.9b23019Google Scholar29Surface-Dependent Stability of the Interface between Garnet Li7La3Zr2O12 and the Li Metal in the All-Solid-State Battery from First-Principles CalculationsGao, Bo; Jalem, Randy; Tateyama, YoshitakaACS Applied Materials & Interfaces (2020), 12 (14), 16350-16358CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)The garnet-type Li7La3Zr2O12 (LLZO) solid electrolyte is of particular interest because of its good chem. stability under atm. condition, suitable for practical all-solid-state batteries (ASSBs). However, recent works obsd. electrochem. instability at the LLZO/Li interfaces. Herein, the origin is revealed of the instability by performing a comprehensive first-principles investigation with a high-throughput interface structure search scheme, based on the d. functional theory framework. Based on the constructed phase diagrams of low-index surfaces, it was found that the coordinatively unsatd. (i.e. coordination no. < 6) Zr sites exist widely on the low-energy LLZO surfaces. These undercoordinated Zr sites are reduced once the LLZO surface is in contact with the Li metal, leading to chem. instability of the LLZO/Li interface. Besides, the calcd. formation and adhesion energies of interfaces suggest that the Li wettability on the LLZO surface is dependent on the termination structure. The employment of the approaches such as by controlling the synthesis atm. are needed for preventing the redn. of LLZO against the Li metal. The present anal. with comprehensive first-principles calcns. provides a novel perspective for the rational optimization of the interface between LLZO electrolyte and Li metal anode in the ASSB.
- 30Fingerle, M.; Buchheit, R.; Sicolo, S.; Albe, K.; Hausbrand, R. Reaction and Space Charge Layer Formation at the LiCoO2–LiPON Interface: Insights on Defect Formation and Ion Energy Level Alignment by a Combined Surface Science–Simulation Approach. Chem. Mater. 2017, 29, 7675– 7685, DOI: 10.1021/acs.chemmater.7b00890Google Scholar30Reaction and Space Charge Layer Formation at the LiCoO2-LiPON Interface: Insights on Defect Formation and Ion Energy Level Alignment by a Combined Surface Science-Simulation ApproachFingerle, Mathias; Buchheit, Roman; Sicolo, Sabrina; Albe, Karsten; Hausbrand, ReneChemistry of Materials (2017), 29 (18), 7675-7685CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)In this contribution, we investigate the formation and evolution of LiCoO2-LiPON interfaces upon annealing using photoelectron spectroscopy. We identify interlayer compds. related to the deposition process and study the chem. reactions leading to interlayer formation. Based on the structure of the pristine interface as well as on its evolution upon annealing, we relate reaction layer and space charge layer formation to chem. potential differences between the two materials. The results are discussed in terms of a combined Li-ion and electron interface energy level scheme providing insights into fundamental charge transfer processes. In constructing the energy level alignment, we take into account calcd. defect formation energies of lithium in the cathode and solid electrolyte.
- 31Nakamura, T.; Amezawa, K.; Kulisch, J.; Zeier, W. G.; Janek, J. Guidelines for All-Solid-State Battery Design and Electrode Buffer Layers Based on Chemical Potential Profile Calculation. ACS Appl. Mater. Interfaces 2019, 11, 19968– 19976, DOI: 10.1021/acsami.9b03053Google Scholar31Guidelines for All-Solid-State Battery Design and Electrode Buffer Layers Based on Chemical Potential Profile CalculationNakamura, Takashi; Amezawa, Koji; Kulisch, Jorn; Zeier, Wolfgang G.; Janek, JurgenACS Applied Materials & Interfaces (2019), 11 (22), 19968-19976CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)Protective coatings on cathode active materials have become paramount for the implementation of solid-state batteries; however, the development of coatings lacks the understanding of the necessary coating properties. In this study, guidelines for the design of solid electrolytes and electrode coatings in all-solid-state batteries are proposed from the viewpoint of the steady-state Li chem. potential profile across the battery cell. The model calcn. of the (electro)chem. potential profile in all-solid-state batteries is established by considering the steady-state mixed ionic and electronic conduction in the solid electrolyte under the assumption of local equil. For quant. discussion, the potential profiles within oxygen ion conductors are calcd. instead of Li/Na ion conductors as their partial electronic conductivities have not been reported so far in sufficient detail. Based on the calcd. chem. potential profile, two main conclusions are obtained: the decisive factor for the formation of the chem. potential profile of the neutral mobile component (e.g., oxygen or lithium) in the solid electrolyte is its electronic cond. (and the activity dependence) and a particularly large potential drop is formed in a region where the electronic cond. becomes small. While these conclusions are valid and general for any solid electrolyte device, they are particularly important for the design of protective coatings and the understanding of the functionality of self-assembled solid electrolyte interphases in all-solid-state batteries. To protect the solid electrolyte from decompn. by redn./oxidn. at the anode/cathode interfaces, a sufficient chem. potential drop is necessary within the coating layer or directly at the interphase layer. To achieve this situation, the coating/interphase materials need to have a lower electronic cond. than the solid electrolyte.
- 32Leung, K. DFT Modelling of Explicit Solid–Solid Interfaces in Batteries: Methods and Challenges. Phys. Chem. Chem. Phys. 2020, 22, 10412– 10425, DOI: 10.1039/C9CP06485KGoogle Scholar32DFT modelling of explicit solid-solid interfaces in batteries: methods and challengesLeung, KevinPhysical Chemistry Chemical Physics (2020), 22 (19), 10412-10425CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)D. Functional Theory (DFT) calcns. of electrode material properties in high energy d. storage devices like lithium batteries have been std. practice for decades. In contrast, DFT modeling of explicit interfaces in batteries arguably lacks universally adopted methodol. and needs further conceptual development. In this paper, we focus on solid-solid interfaces, which are ubiquitous not just in all-solid state batteries; liq.-electrolyte-based batteries often rely on thin, solid passivating films on electrode surfaces to function. We use metal anode calcns. to illustrate that explicit interface models are crit. for elucidating contact potentials, elec. fields at interfaces, and kinetic stability with respect to parasitic reactions. The examples emphasize three key challenges: (1) the "dirty" nature of most battery electrode surfaces; (2) voltage calibration and control; and (3) the fact that interfacial structures are governed by kinetics, not thermodn. To meet these challenges, developing new computational techniques and importing insights from other electrochem. disciplines will be beneficial.
- 33Haruyama, J.; Sodeyama, K.; Tateyama, Y. Cation Mixing Properties toward Co Diffusion at the LiCoO2 Cathode/Sulfide Electrolyte Interface in a Solid-State Battery. ACS Appl. Mater. Interfaces 2017, 9, 286– 292, DOI: 10.1021/acsami.6b08435Google Scholar33Cation Mixing Properties toward Co Diffusion at the LiCoO2 Cathode/Sulfide Electrolyte Interface in a Solid-State BatteryHaruyama, Jun; Sodeyama, Keitaro; Tateyama, YoshitakaACS Applied Materials & Interfaces (2017), 9 (1), 286-292CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)All-solid-state Li-ion batteries (ASS-LIBs) are expected to be the next-generation battery, however, their large interfacial resistance hinders their widespread application. To understand and resolve the possible causes of this resistance, we examd. mutual diffusion properties of the cation elements at LiCoO2 (LCO) cathode/β-Li3PS4 (LPS) solid electrolyte interface as a representative system as well as the effect of a LiNbO3 buffer layer by first-principles calcns. Evaluating energies of exchanging ions between the cathode and the electrolyte, we found that the mixing of Co and P is energetically preferable to the unmixed states at the LCO/LPS interface. We also demonstrated that the interposition of the buffer layer suppresses such mixing because the exchange of Co and Nb is energetically unfavorable. Detailed analyses of the defect levels and the exchange energies by using the individual bulk crystals as well as the interfaces suggest that the lower interfacial states in the energy gap can make a major contribution to the stabilization of the Co - P exchange, although the anion bonding preference of Co and P as well as the electrostatic interactions may have effects as well. Finally, the Co - P exchanges induce interfacial Li sites with low chem. potentials, which enhance the growth of the Li depletion layer. These atomistic understandings can be meaningful for the development of ASS-LIBs with smaller interfacial resistances.
- 34Leung, K.; Leenheer, A. How Voltage Drops Are Manifested by Lithium Ion Configurations at Interfaces and in Thin Films on Battery Electrodes. J. Phys. Chem. C 2015, 119, 10234– 10246, DOI: 10.1021/acs.jpcc.5b01643Google Scholar34How Voltage Drops Are Manifested by Lithium Ion Configurations at Interfaces and in Thin Films on Battery ElectrodesLeung, Kevin; Leenheer, AndrewJournal of Physical Chemistry C (2015), 119 (19), 10234-10246CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)Battery electrode surfaces are generally coated with electronically insulating solid films of thickness 1-50 nm. Both electrons and Li+ can move at the electrode-surface film interface in response to the voltage, which adds complexity to the "elec. double layer" (EDL). We apply D. Functional Theory (DFT) to investigate how the applied voltage is manifested as changes in the EDL at at. length scales, including charge sepn. and interfacial dipole moments. Illustrating examples include Li3PO4, Li2CO3, and LixMn2O4 thin films on Au(111) surfaces under ultrahigh vacuum conditions. Adsorbed org. solvent mols. can strongly reduce voltages predicted in vacuum. We propose that manipulating surface dipoles, seldom discussed in battery studies, may be a viable strategy to improve electrode passivation. We also distinguish the computed potential governing electrons, which is the actual or instantaneous voltage, and the "lithium cohesive energy"-based voltage governing Li content widely reported in DFT calcns., which is a slower-responding self-consistency criterion at interfaces. This distinction is crit. for a comprehensive description of electrochem. activities on electrode surfaces, including Li+ insertion dynamics, parasitic electrolyte decompn., and electrodeposition at overpotentials.
- 35Wang, Y.; Lv, J.; Zhu, L.; Ma, Y. Crystal Structure Prediction via Particle-Swarm Optimization. Phys. Rev. B: Condens. Matter Mater. Phys. 2010, 82, 094116, DOI: 10.1103/PhysRevB.82.094116Google Scholar35Crystal structure prediction via particle-swarm optimizationWang, Yanchao; Lv, Jian; Zhu, Li; Ma, YanmingPhysical Review B: Condensed Matter and Materials Physics (2010), 82 (9), 094116/1-094116/8CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)A method is developed for crystal structure prediction from scratch through particle-swarm optimization (PSO) algorithm within the evolutionary scheme. PSO technique is different with the genetic algorithm and has apparently avoided the use of evolution operators (e.g., crossover and mutation). The approach is based on an efficient global minimization of free-energy surfaces merging total-energy calcns. via PSO technique and requires only chem. compns. for a given compd. to predict stable or metastable structures at given external conditions (e.g., pressure). A particularly devised geometrical structure parameter which allows the elimination of similar structures during structure evolution was implemented to enhance the structure search efficiency. The application of designed variable unit-cell size technique has greatly reduced the computational cost. Moreover, the symmetry constraint imposed in the structure generation enables the realization of diverse structures, leads to significantly reduced search space and optimization variables, and thus fastens the global structure convergence. The PSO algorithm was successfully applied to the prediction of many known systems (e.g., elemental, binary, and ternary compds.) with various chem.-bonding environments (e.g., metallic, ionic, and covalent bonding). The high success rate demonstrates the reliability of this methodol. and illustrates the promise of PSO as a major technique on crystal structure detn.
- 36Wang, Y.; Lv, J.; Zhu, L.; Ma, Y. CALYPSO: A Method for Crystal Structure Prediction. Comput. Phys. Commun. 2012, 183, 2063– 2070, DOI: 10.1016/j.cpc.2012.05.008Google Scholar36CALYPSO: A method for crystal structure predictionWang, Yanchao; Lv, Jian; Zhu, Li; Ma, YanmingComputer Physics Communications (2012), 183 (10), 2063-2070CODEN: CPHCBZ; ISSN:0010-4655. (Elsevier B.V.)The authors have developed a software package CALYPSO (Crystal structure Anal. by Particle Swarm Optimization) to predict the energetically stable/metastable crystal structures of materials at given chem. compns. and external conditions (e.g., pressure). The CALYPSO method is based on several major techniques (e.g. particle-swarm optimization algorithm, symmetry constraints on structural generation, bond characterization matrix on elimination of similar structures, partial random structures per generation on enhancing structural diversity, and penalty function, etc.) for global structural minimization from scratch. All of these techniques are crit. to the prediction of global stable structure. The authors have implemented these techniques into the CALYPSO code. Testing of the code on many known and unknown systems shows high efficiency and the highly successful rate of this CALYPSO method. The authors focus on descriptions of the implementation of CALYPSO code and why it works.
- 37Gao, B.; Gao, P.; Lu, S.; Lv, J.; Wang, Y.; Ma, Y. Interface Structure Prediction via CALYPSO Method. Sci. Bull. 2019, 64, 301– 309, DOI: 10.1016/j.scib.2019.02.009Google Scholar37Interface structure prediction via CALYPSO methodGao, Bo; Gao, Pengyue; Lu, Shaohua; Lv, Jian; Wang, Yanchao; Ma, YanmingScience Bulletin (2019), 64 (5), 301-309CODEN: SBCUA5; ISSN:2095-9281. (Elsevier B.V.)The atomistic structures of solid-solid interfaces are of fundamental interests for understanding phys. properties of interfacial materials. However, detn. of interface structures faces a substantial challenge, both exptl. and theor. Here, we propose an efficient method for predicting interface structures via the generalization of our inhouse developed CALYPSO method for structure prediction. We devised a lattice match toolkit that allows us to automatically search for the optimal lattice-matched superlattice for construction of the interface structures. In addn., bonding constraints (e.g., constraints on interat. distances and coordination nos. of atoms) are imposed to generate better starting interface structures by taking advantages of the known bonding environment derived from the stable bulk phases. The interface structures evolve by following interfacially confined swarm intelligence algorithm, which is known to be efficient for exploration of potential energy surface. The method was validated by correctly predicting a no. of known interface structures with only given information of two parent solids. The application of the developed method leads to prediction of two unknown grain boundary (GB) structures (r-GB and p-GB) of rutile TiO2 Σ5(2 1 0) under an O reducing atm. that contained Ti3+ as the result of O defects. Further calcns. revealed that the intrinsic band gap of p-GB is reduced to 0.7 eV owing to substantial broadening of the Ti-3d interfacial levels from Ti3+ centers. Our results demonstrated that introduction of grain boundaries is an effective strategy to engineer the electronic properties and thus enhance the visible-light photoactivity of TiO2.
- 38Qian, D.; Hinuma, Y.; Chen, H.; Du, L.-S.; Carroll, K. J.; Ceder, G.; Grey, C. P.; Meng, Y. S. Electronic Spin Transition in Nanosize Stoichiometric Lithium Cobalt Oxide. J. Am. Chem. Soc. 2012, 134, 6096– 6099, DOI: 10.1021/ja300868eGoogle Scholar38Electronic Spin Transition in Nanosize Stoichiometric Lithium Cobalt OxideQian, Danna; Hinuma, Yoyo; Chen, Hailong; Du, Lin-Shu; Carroll, Kyler J.; Ceder, Gerbrand; Grey, Clare P.; Meng, Ying S.Journal of the American Chemical Society (2012), 134 (14), 6096-6099CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)A change in the electronic spin state of the surfaces relevant to Li (de)intercalation of nanosized stoichiometric LiCo(III)O2 from low-spin to intermediate and high spin was obsd. for the 1st time. These surfaces are relevant for Li (de)intercalation. From DFT calcns. with Hubbard U correction, the surface energies of the layered Li Co oxide can be lowered as a consequence of the spin change. The crystal field splitting of Co d orbitals is modified at the surface due to missing Co-O bonds. The electronic spin transition also has an impact on Co(III)-Co(IV) redox potential, as revealed by the change in the Li (de)intercalation voltage profile in a Li half cell.
- 39Yang, Y.; Wu, Q.; Cui, Y.; Chen, Y.; Shi, S.; Wang, R.-Z.; Yan, H. Elastic Properties, Defect Thermodynamics, Electrochemical Window, Phase Stability, and Li+ Mobility of Li3PS4: Insights from First-Principles Calculations. ACS Appl. Mater. Interfaces 2016, 8, 25229– 25242, DOI: 10.1021/acsami.6b06754Google Scholar39Elastic Properties, Defect Thermodynamics, Electrochemical Window, Phase Stability, and Li+ Mobility of Li3PS4: Insights from First-Principles CalculationsYang, Yanhan; Wu, Qu; Cui, Yanhua; Chen, Yongchang; Shi, Siqi; Wang, Ru-Zhi; Yan, HuiACS Applied Materials & Interfaces (2016), 8 (38), 25229-25242CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)The improved ionic cond. (1.64 × 10-4 S cm-1 at room temp.) and excellent electrochem. stability of nanoporous β-Li3PS4 make it one of the promising candidates for rechargeable all-solid-state lithium-ion battery electrolytes. Here, elastic properties, defect thermodn., phase diagram, and Li+ migration mechanism of Li3PS4 (both γ and β phases) are examd. via the first-principles calcns. Results indicate that both γ- and β-Li3PS4 phases are ductile while γ-Li3PS4 is harder under vol. change and shear stress than β-Li3PS4. The electrochem. window of Li3PS4 ranges from 0.6 to 3.7 V, and thus the exptl. excellent stability (>5 V) is proposed due to the passivation phenomenon. The dominant diffusion carrier type in Li3PS4 is identified over its electrochem. window. In γ-Li3PS4 the direct-hopping of Lii+ along the [001] is energetically more favorable than other diffusion processes, whereas in β-Li3PS4 the knock-off diffusion of Lii+ along the [010] has the lowest migration barrier. The ionic cond. is evaluated from the concn. and the mobility calcns. using the Nernst-Einstein relationship and compared with the available exptl. results. According to our calcd. results, the Li+ prefers to transport along the [010] direction. It is suggested that the enhanced ionic cond. in nanostructured β-Li3PS4 is due to the larger possibility of contiguous (010) planes provided by larger nanoporous β-Li3PS4 particles. By a series of motivated and closely linked calcns., we try to provide a portable method, by which researchers could gain insights into the physicochem. properties of solid electrolyte.
- 40Sanna, S.; Schmidt, W. G. Lithium Niobate X -Cut, Y -Cut, and Z -Cut Surfaces from Ab Initio Theory. Phys. Rev. B: Condens. Matter Mater. Phys. 2010, 81, 214116, DOI: 10.1103/PhysRevB.81.214116Google Scholar40Lithium niobate X-cut, Y-cut, and Z-cut surfaces from ab initio theorySanna, Simone; Schmidt, Wolf GeroPhysical Review B: Condensed Matter and Materials Physics (2010), 81 (21), 214116/1-214116/11CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)D.-functional theory calcns. of the LiNbO3 (2110), (1100), and (0001) surfaces, commonly referred to as X, Y, and Z cuts, are presented. In case of the Z cut, we find a pronounced dependence of the surface structure and stoichiometry on the direction of the ferroelec. polarization. In contrast, the influence of the chem. potentials of the surface constituents is limited. Rather electrostatics governs the surface stability. Different from the Z cut, the stoichiometry of the X cut and Y cut is clearly dependent on the prepn. conditions. The surface charge obsd. for the nominal nonpolar Y cut is traced back to the formation of a strong surface dipole.
- 41Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 1996, 77, 3865– 3868, DOI: 10.1103/PhysRevLett.77.3865Google Scholar41Generalized gradient approximation made simplePerdew, John P.; Burke, Kieron; Ernzerhof, MatthiasPhysical Review Letters (1996), 77 (18), 3865-3868CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)Generalized gradient approxns. (GGA's) for the exchange-correlation energy improve upon the local spin d. (LSD) description of atoms, mols., and solids. We present a simple derivation of a simple GGA, in which all parameters (other than those in LSD) are fundamental consts. Only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked. Improvements over PW91 include an accurate description of the linear response of the uniform electron gas, correct behavior under uniform scaling, and a smoother potential.
- 42Kresse, G.; Joubert, D. From Ultrasoft Pseudopotentials to the Projector Augmented-Wave Method. Phys. Rev. B: Condens. Matter Mater. Phys. 1999, 59, 1758– 1775, DOI: 10.1103/PhysRevB.59.1758Google Scholar42From ultrasoft pseudopotentials to the projector augmented-wave methodKresse, G.; Joubert, D.Physical Review B: Condensed Matter and Materials Physics (1999), 59 (3), 1758-1775CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)The formal relationship between ultrasoft (US) Vanderbilt-type pseudopotentials and Blochl's projector augmented wave (PAW) method is derived. The total energy functional for US pseudopotentials can be obtained by linearization of two terms in a slightly modified PAW total energy functional. The Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional. A simple way to implement the PAW method in existing plane-wave codes supporting US pseudopotentials is pointed out. In addn., crit. tests are presented to compare the accuracy and efficiency of the PAW and the US pseudopotential method with relaxed-core all-electron methods. These tests include small mols. (H2, H2O, Li2, N2, F2, BF3, SiF4) and several bulk systems (diamond, Si, V, Li, Ca, CaF2, Fe, Co, Ni). Particular attention is paid to the bulk properties and magnetic energies of Fe, Co, and Ni.
- 43Blöchl, P. E. Projector Augmented-Wave Method. Phys. Rev. B: Condens. Matter Mater. Phys. 1994, 50, 17953– 17979, DOI: 10.1103/PhysRevB.50.17953Google Scholar43Projector augmented-wave methodBlochlPhysical review. B, Condensed matter (1994), 50 (24), 17953-17979 ISSN:0163-1829.There is no expanded citation for this reference.
- 44Anisimov, V. I.; Zaanen, J.; Andersen, O. K. Band Theory and Mott Insulators: Hubbard U Instead of Stoner I. Phys. Rev. B: Condens. Matter Mater. Phys. 1991, 44, 943– 954, DOI: 10.1103/PhysRevB.44.943Google Scholar44Band theory and Mott insulators: Hubbard U instead of Stoner IAnisimov, V. I.; Zaanen, Jan; Andersen, Ole K.Physical Review B: Condensed Matter and Materials Physics (1991), 44 (3), 943-54CODEN: PRBMDO; ISSN:0163-1829.The authors propose a form for the exchange-correlation potential in local-d. band theory, appropriate to Mott insulators. The idea is to use the "constrained-local-d.-approxn." Hubbard parameter U as the quantity relating the single-particle potentials-to the magnetic- (and orbital-) order parameters. The authors' energy functional is that of the local-d. approxn. plus the mean-field approxn. to the remaining part of the U term. They argue that such a method should make sense, if one accepts the Hubbard model and the success of constrained-local-d.-approxn. parameter calcns. By using this ab initio scheme, they find that all late-3d-transition-metal monoxides, as well as the parent compds. of the high-Tc compds., are large-gap magnetic insulators of the charge-transfer type. Further, the method predicts that LiNiO2 is a low-spin ferromagnet and NiS a local-moment p-type metal. The present version of the scheme fails for the early-3d-transition-metal monoxides and for the late 3d transition metals.
- 45Zhou, F.; Cococcioni, M.; Marianetti, C. A.; Morgan, D.; Ceder, G. First-Principles Prediction of Redox Potentials in Transition-Metal Compounds with LDA+U. Phys. Rev. B: Condens. Matter Mater. Phys. 2004, 70, 235121, DOI: 10.1103/PhysRevB.70.235121Google Scholar45First-principles prediction of redox potentials in transition-metal compounds with LDA+UZhou, F.; Cococcioni, M.; Marianetti, C. A.; Morgan, D.; Ceder, G.Physical Review B: Condensed Matter and Materials Physics (2004), 70 (23), 235121/1-235121/8CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)First-principles calcns. within the local d. approxn. (LDA) or generalized gradient approxn. (GGA), though very successful, are known to underestimate redox potentials, such as those at which lithium intercalates in transition metal compds. We argue that this inaccuracy is related to the lack of cancellation of electron self-interaction errors in LDA/GGA and can be improved by using the DFT + U method with a self-consistent evaluation of the U parameter. We show that, using this approach, the exptl. lithium intercalation voltages of a no. of transition metal compds., including the olivine LixMPO4 (M = Mn, Fe Co, Ni), layered LixMO2 (x = Co, Ni) and spinel-like LixM2O4 (M = Mn, Co), can be reproduced accurately.
- 46Ohta, N.; Takada, K.; Sakaguchi, I.; Zhang, L.; Ma, R.; Fukuda, K.; Osada, M.; Sasaki, T. LiNbO3-Coated LiCoO2 as Cathode Material for All Solid-State Lithium Secondary Batteries. Electrochem. Commun. 2007, 9, 1486– 1490, DOI: 10.1016/j.elecom.2007.02.008Google Scholar46LiNbO3-coated LiCoO2 as cathode material for all solid-state lithium secondary batteriesOhta, Narumi; Takada, Kazunori; Sakaguchi, Isao; Zhang, Lianqi; Ma, Renzhi; Fukuda, Katsutoshi; Osada, Minoru; Sasaki, TakayoshiElectrochemistry Communications (2007), 9 (7), 1486-1490CODEN: ECCMF9; ISSN:1388-2481. (Elsevier B.V.)The enhancement of the high-rate capabilities for solid-state Li secondary batteries is reported. A nanometer thick LiNbO3 layer was interposed between LiCoO2 and the solid sulfide electrolyte as buffer layer. This decreased the interfacial resistance in the cathode and enhanced the high-rate capabilities of the batteries - this can enable design of Li secondary batteries free from safety issues.
- 47Fu, L.; Chen, C.-C.; Samuelis, D.; Maier, J. Thermodynamics of Lithium Storage at Abrupt Junctions: Modeling and Experimental Evidence. Phys. Rev. Lett. 2014, 112, 208301, DOI: 10.1103/physrevlett.112.208301Google Scholar47Thermodynamics of lithium storage at abrupt junctions: modeling and experimental evidenceFu, Lijun; Chen, Chia-Chin; Samuelis, Dominik; Maier, JoachimPhysical Review Letters (2014), 112 (20), 208301/1-208301/5, 5 pp.CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)We present the thermodn. modeling and exptl. evidence of the occurrence of lithium storage at abrupt junctions, which describes the transition from an electrostatic capacitor to a chem. capacitor. In both Ru:Li2O and Ni:LiF systems, the functionalities and extd. parameters are in good agreement with the thermodn. model, based on the dependence of the storage capacity on open-circuit voltage. Moreover, it is set out that a complete understanding of a conventional storage mechanism requires unifying both the space charge and bulk storage for a nanocryst. electroactive electrode.
Cited By
Smart citations by scite.ai include citation statements extracted from the full text of the citing article. The number of the statements may be higher than the number of citations provided by ACS Publications if one paper cites another multiple times or lower if scite has not yet processed some of the citing articles.
This article is cited by 47 publications.
- Zizhen Zhou, Huu Duc Luong, Bo Gao, Toshiyuki Momma, Yoshitaka Tateyama. LiNbO3 and LiTaO3 Coating Effects on the Interface of the LiCoO2 Cathode: A DFT Study of Li-Ion Transport. ACS Applied Materials & Interfaces 2024, 16
(32)
, 42093-42099. https://doi.org/10.1021/acsami.4c05737
- Kana Onoue, Akira Nasu, Kazuhiko Matsumoto, Rika Hagiwara, Hiroaki Kobayashi, Masaki Matsui. Trigger of the Highly Resistive Layer Formation at the Cathode–Electrolyte Interface in All-Solid-State Lithium Batteries Using a Garnet-Type Lithium-Ion Conductor. ACS Applied Materials & Interfaces 2023, 15
(45)
, 52333-52341. https://doi.org/10.1021/acsami.3c07177
- Ahmad Sohib, Muhammad Alief Irham, Jotti Karunawan, Sigit Puji Santosa, Octia Floweri, Ferry Iskandar. Interface Analysis of LiCl as a Protective Layer of Li1.3Al0.3Ti1.7(PO4)3 for Electrochemically Stabilized All-Solid-State Li-Metal Batteries. ACS Applied Materials & Interfaces 2023, 15
(13)
, 16562-16570. https://doi.org/10.1021/acsami.2c18852
- Joo Young Lee, Sungwoo Noh, Ju Yeong Seong, Sangheon Lee, Yong Joon Park. Suppressing Unfavorable Interfacial Reactions Using Polyanionic Oxides as Efficient Buffer Layers: Low-Cost Li3PO4 Coatings for Sulfide-Electrolyte-Based All-Solid-State Batteries. ACS Applied Materials & Interfaces 2023, 15
(10)
, 12998-13011. https://doi.org/10.1021/acsami.2c21511
- Yusuke Morino, Satoshi Kanada. Degradation Analysis by X-ray Absorption Spectroscopy for LiNbO3 Coating of Sulfide-Based All-Solid-State Battery Cathode. ACS Applied Materials & Interfaces 2023, 15
(2)
, 2979-2984. https://doi.org/10.1021/acsami.2c19414
- Zizhen Zhou, Dewei Chu, Bo Gao, Toshiyuki Momma, Yoshitaka Tateyama, Claudio Cazorla. Tuning the Electronic, Ion Transport, and Stability Properties of Li-rich Manganese-based Oxide Materials with Oxide Perovskite Coatings: A First-Principles Computational Study. ACS Applied Materials & Interfaces 2022, 14
(32)
, 37009-37018. https://doi.org/10.1021/acsami.2c07560
- Jianwen Liu Fei Zhou Shiquan Wang Rong Zeng . Novel Nitride-Based Electrodes for Solid-State Batteries. , 15-38. https://doi.org/10.1021/bk-2022-1414.ch002
- Andrey Golov, Javier Carrasco. Molecular-Level Insight into the Interfacial Reactivity and Ionic Conductivity of a Li-Argyrodite Li6PS5Cl Solid Electrolyte at Bare and Coated Li-Metal Anodes. ACS Applied Materials & Interfaces 2021, 13
(36)
, 43734-43745. https://doi.org/10.1021/acsami.1c12753
- Diana Chaykina, Meena Ghosh, Ömer Ulaş Kudu. Critical outlook on separator layers for solid-state lithium batteries: Solid electrolyte materials, anode interface engineering, & scalable separator production. Journal of Power Sources 2025, 643 , 237014. https://doi.org/10.1016/j.jpowsour.2025.237014
- Bin Man, Yulong Zeng, Qingrui Liu, Yinwen Chen, Xin Li, Wenjing Luo, Zikang Zhang, Changliang He, Min Jie, Sijie Liu. A Comprehensive Review of Sulfide Solid-State Electrolytes: Properties, Synthesis, Applications, and Challenges. Crystals 2025, 15
(6)
, 492. https://doi.org/10.3390/cryst15060492
- Chenglin Cai, Kongjun Zhu, Yu Rao, Zhihan Kong, Ziyun Li, Xiaorao Wu, Yuqing Yang, Miaomiao Huang, Heng Zhou, Kang Yan, Jing Wang, Feng Shi, Jun Guo. Ternary doping enhances the moisture and electrochemical stability of Li5.5PS4.5Cl1.5 solid-state electrolyte. Journal of Materials Science: Materials in Electronics 2025, 36
(9)
https://doi.org/10.1007/s10854-025-14581-w
- Jonas Spychala, Christoph Mandl, Katharina Hogrefe, H. Martin R. Wilkening, Bernhard Gadermaier. Morphology-dependent Li
+
ion dynamics in X-ray amorphous and crystalline Li
3
PS
4
prepared by solvent-assisted synthesis. Dalton Transactions 2025, 54
(6)
, 2283-2293. https://doi.org/10.1039/D4DT02636E
- Yanchen Liu, Yang Lu, Zongliang Zhang, Bin Xu, Fangbo He, Yang Liu, Yongle Chen, Kun Zhang, Fangyang Liu. High-areal-capacity and long-life sulfide-based all-solid-state lithium battery achieved by regulating surface-to-bulk oxygen activity. Journal of Energy Chemistry 2025, 101 , 795-807. https://doi.org/10.1016/j.jechem.2024.10.022
- Duo Yang, Pengchong Xu, Changgui Xu, Qi Zhou, Ningbo Liao. Highly stable silicon oxycarbide all-solid-state batteries enabled by machined learning accelerated screening of oxides and sulfides electrolytes. Journal of Colloid and Interface Science 2025, 677 , 130-139. https://doi.org/10.1016/j.jcis.2024.07.200
- Govind Kumar Mishra, Manoj Gautam, K. Bhawana, Chhotelal Sah Kalwar, Manisha Patro, Anshu, Sagar Mitra. Exploring Chemical and Electrochemical Limitations in Sulfide Solid State Electrolytes: A Critical Review on Current Status and Manufacturing Scope. Chemistry – A European Journal 2024, 30
(71)
https://doi.org/10.1002/chem.202402510
- Shanyan Huang, Bi Luo, Zixun Zhang, Qi Wang, Guihui Yu, Xudong Bu, Zheng Huang, Xiaowei Wang, Wei-Li Song, Jiafeng Zhang, Shuqiang Jiao. Effect of crystal morphology of nickel-rich cathode materials on electrochemical stability and ion transport kinetics of sulfide-based all-solid-state batteries. Chinese Chemical Letters 2024, 1 , 110729. https://doi.org/10.1016/j.cclet.2024.110729
- Israel Temprano, Javier Carrasco, Matthieu Bugnet, Ivan T. Lucas, Jigang Zhou, Robert S. Weatherup, Christopher A. O'Keefe, Zachary Ruff, Jiahui Xu, Nicolas Folastre, Jian Wang, Antonin Gajan, Arnaud Demortière. Advanced methods for characterizing battery interfaces: Towards a comprehensive understanding of interfacial evolution in modern batteries. Energy Storage Materials 2024, 73 , 103794. https://doi.org/10.1016/j.ensm.2024.103794
- Javier Carrasco. A theoretical perspective on solid-state ionic interfaces. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences 2024, 382
(2281)
https://doi.org/10.1098/rsta.2023.0313
- Xiumei Kang, Hongbin Lin, Guigui Xu, Jianming Tao, Yue Chen, Kehua Zhong, Jian-Min Zhang, Zhigao Huang. Space charge layers and interface potentials in
Li
/
γ
−
Li
3
PO
4
/
Li
x
CoO
2
solid-state batteries: Insights from a first-principles-informed thermodynamic study. Physical Review Materials 2024, 8
(10)
https://doi.org/10.1103/PhysRevMaterials.8.105402
- Yusuke Morino, Kentaro Takase, Kazuhiro Kamiguchi, Daisuke Ito. Ethanol‐Based Solution Synthesis of a Functionalized Sulfide Solid Electrolyte: Investigation and Application. Batteries & Supercaps 2024, 7
(10)
https://doi.org/10.1002/batt.202400264
- Xin Gao, Zheng Zhen, Jiayi Chen, Runjing Xu, Xiantai Zeng, Jinliang Su, Ya Chen, Xiaodong Chen, Lifeng Cui. Interface stability of cathode for all-solid-state lithium batteries based on sulfide electrolyte: Current insights and future directions. Chemical Engineering Journal 2024, 491 , 152010. https://doi.org/10.1016/j.cej.2024.152010
- Da Wang, Xiaobin Yin, Jianfang Wu, Yaqiao Luo, Siqi Shi. All-Solid-State Lithium Cathode/Electrolyte Interfacial Resistance: From Space-Charge Layer Model to Characterization and Simulation. Acta Physico-Chimica Sinica 2024, 40
(7)
, 2307029. https://doi.org/10.3866/PKU.WHXB202307029
- Yanchen Liu, Zongliang Zhang, Siliang Liu, Yang Liu, Zhi Zhuang, Fangyang Liu. Enhanced all-solid-state battery performance through in-situ construction of interface modification layer. Journal of Power Sources 2024, 602 , 234187. https://doi.org/10.1016/j.jpowsour.2024.234187
- Chuntian Cao, Matthew R. Carbone, Cem Komurcuoglu, Jagriti S. Shekhawat, Kerry Sun, Haoyue Guo, Sizhan Liu, Ke Chen, Seong-Min Bak, Yonghua Du, Conan Weiland, Xiao Tong, Daniel A. Steingart, Shinjae Yoo, Nongnuch Artrith, Alexander Urban, Deyu Lu, Feng Wang. Atomic insights into the oxidative degradation mechanisms of sulfide solid electrolytes. Cell Reports Physical Science 2024, 5
(4)
, 101909. https://doi.org/10.1016/j.xcrp.2024.101909
- Hongbin Lin, Xiumei Kang, Guigui Xu, Yue Chen, Kehua Zhong, Jian-Min Zhang, Zhigao Huang. A synergetic promotion of surface stability for high-voltage LiCoO
2
by multi-element surface doping: a first-principles study. Physical Chemistry Chemical Physics 2024, 26
(5)
, 4174-4183. https://doi.org/10.1039/D3CP04130A
- Ziheng Lu, Bonan Zhu. Crystal Structure Prediction for Battery Materials. 2024, 187-210. https://doi.org/10.1007/978-3-031-47303-6_7
- Yoshitaka Tateyama. Microscopic Ion Transport in Electrodes, Solid Electrolytes, and Their Interfaces Via First-Principles Calculations. 2024, 335-349. https://doi.org/10.1007/978-981-97-6039-8_29
- Shusuke Kasamatsu. Ab Initio Thermodynamics of Space Charge Formation at Solid State Electrochemical Interfaces. 2024, 387-400. https://doi.org/10.1007/978-981-97-6039-8_33
- Zhan Wu, Xiaohan Li, Chao Zheng, Zheng Fan, Wenkui Zhang, Hui Huang, Yongping Gan, Yang Xia, Xinping He, Xinyong Tao, Jun Zhang. Interfaces in Sulfide Solid Electrolyte-Based All-Solid-State Lithium Batteries: Characterization, Mechanism and Strategy. Electrochemical Energy Reviews 2023, 6
(1)
https://doi.org/10.1007/s41918-022-00176-0
- Rajashree Konar, Sandipan Maiti, Netanel Shpigel, Doron Aurbach. Reviewing failure mechanisms and modification strategies in stabilizing high-voltage LiCoO2 cathodes beyond 4.55V. Energy Storage Materials 2023, 63 , 103001. https://doi.org/10.1016/j.ensm.2023.103001
- Anton Block, Chie Hoon Song. Exploring the potential of material information in patent data: The case of solid-state batteries. Journal of Energy Storage 2023, 71 , 108123. https://doi.org/10.1016/j.est.2023.108123
- Jianhui Zheng, Xinxin Zhu, Liguang Wang, Jun Lu, Tianpin Wu. Insights into interfacial physiochemistry in sulfide solid-state batteries: a review. Materials Chemistry Frontiers 2023, 7
(20)
, 4810-4832. https://doi.org/10.1039/D3QM00400G
- Dongsheng Ren, Languang Lu, Rui Hua, Gaolong Zhu, Xiang Liu, Yuqiong Mao, Xinyu Rui, Shan Wang, Bosheng Zhao, Hao Cui, Min Yang, Haorui Shen, Chen-Zi Zhao, Li Wang, Xiangming He, Saiyue Liu, Yukun Hou, Tiening Tan, Pengbo Wang, Yoshiaki Nitta, Minggao Ouyang. Challenges and opportunities of practical sulfide-based all-solid-state batteries. eTransportation 2023, 18 , 100272. https://doi.org/10.1016/j.etran.2023.100272
- Wenru Li, Shu Zhang, Weijie Zheng, Jun Ma, Lin Li, Yue Zheng, Deye Sun, Zheng Wen, Zhen Liu, Yaojin Wang, Guangzu Zhang, Guanglei Cui. Self‐Polarized Organic–Inorganic Hybrid Ferroelectric Cathode Coatings Assisted High Performance All‐Solid‐State Lithium Battery. Advanced Functional Materials 2023, 33
(27)
https://doi.org/10.1002/adfm.202300791
- Alexander Kraytsberg, Yair Ein-Eli. Recent Developments in the Field of Sulfide Ceramic Solid‐State Electrolytes. Energy Technology 2023, 11
(6)
https://doi.org/10.1002/ente.202201291
- Yidong Jiang, Anjie Lai, Jun Ma, Kai Yu, Huipeng Zeng, Guangzhao Zhang, Wei Huang, Chaoyang Wang, Shang‐Sen Chi, Jun Wang, Yonghong Deng. Fundamentals of the Cathode‐Electrolyte Interface in All‐solid‐state Lithium Batteries. ChemSusChem 2023, 16
(9)
https://doi.org/10.1002/cssc.202202156
- Lei Xi, Dechao Zhang, Xijun Xu, Yiwen Wu, Fangkun Li, Shiyan Yao, Min Zhu, Jun Liu. Interface Engineering of All‐Solid‐State Batteries Based on Inorganic Solid Electrolytes. ChemSusChem 2023, 16
(9)
https://doi.org/10.1002/cssc.202202158
- Guigui Xu, Hongbin Lin, Kehua Zhong, Jian-Min Zhang, Zhigao Huang. Li-ion transport at the LiFePO4/γ-Li3PO4 interface and its enhancement through surface nitrogen doping. Journal of Applied Physics 2023, 133
(14)
https://doi.org/10.1063/5.0139019
- Yi Duan, Xiangtao Bai, Tianwei Yu, Yang Rong, Yanlong Wu, Xi Wang, Junfeng Yang, Jiantao Wang. Research progress and prospect in typical sulfide solid-state electrolytes. Journal of Energy Storage 2022, 55 , 105382. https://doi.org/10.1016/j.est.2022.105382
- Juefan Wang, Abhishek A. Panchal, Gopalakrishnan Sai Gautam, Pieremanuele Canepa. The resistive nature of decomposing interfaces of solid electrolytes with alkali metal electrodes. Journal of Materials Chemistry A 2022, 10
(37)
, 19732-19742. https://doi.org/10.1039/D2TA02202H
- Qinkai Feng, Xiuhuai Xie, Miao Zhang, Ningbo Liao. Superior interfacial stability and conductivity of B-doped LiPON electrolyte for LiCoO2 electrode in solid-state lithium batteries. Colloids and Surfaces A: Physicochemical and Engineering Aspects 2022, 648 , 129349. https://doi.org/10.1016/j.colsurfa.2022.129349
- I. V. Maznichenko, P. Buczek, I. Mertig, S. Ostanin. Charge-to-spin conversion in the quasi-two-dimensional electron gas emerging at the hydrogen-doped interface between
LiNbO
3
and
LaAlO
3
. Physical Review Materials 2022, 6
(6)
https://doi.org/10.1103/PhysRevMaterials.6.064001
- Chengdong Wei, Hongtao Xue, Zhou Li, Fenning Zhao, Fuling Tang. Reconstruction and electronic properties of β-Li
3
PS
4
|Li
2
S interface. Journal of Physics D: Applied Physics 2022, 55
(10)
, 105305. https://doi.org/10.1088/1361-6463/ac3c75
- Heebae Kim, Changik Im, Seokgyu Ryu, Yong Jun Gong, Jinil Cho, Seonmi Pyo, Heejun Yun, Jeewon Lee, Jeeyoung Yoo, Youn Sang Kim. Interface Modeling via Tailored Energy Band Alignment: Toward Electrochemically Stabilized All‐Solid‐State Li‐Metal Batteries. Advanced Functional Materials 2022, 32
(9)
https://doi.org/10.1002/adfm.202107555
- Bo Gao, Randy Jalem, Hong‐Kang Tian, Yoshitaka Tateyama. Revealing Atomic‐Scale Ionic Stability and Transport around Grain Boundaries of Garnet Li
7
La
3
Zr
2
O
12
Solid Electrolyte. Advanced Energy Materials 2022, 12
(3)
https://doi.org/10.1002/aenm.202102151
- I. V. Maznichenko, S. Ostanin, I. Mertig, P. Buczek. Emergent quasi-two-dimensional electron gas between
Li
1
±
x
Nb
O
3
and
La
Al
O
3
and its prospectively switchable magnetism. Physical Review Materials 2021, 5
(11)
https://doi.org/10.1103/PhysRevMaterials.5.114001
- Zhen Sun, Yanqing Lai, Na lv, Yaqi Hu, Bingqin Li, Shenghao Jing, Liangxing Jiang, Ming Jia, Jie Li, Shiyou Chen, Fangyang Liu. Boosting the Electrochemical Performance of All‐Solid‐State Batteries with Sulfide Li
6
PS
5
Cl Solid Electrolyte Using Li
2
WO
4
‐Coated LiCoO
2
Cathode. Advanced Materials Interfaces 2021, 8
(15)
https://doi.org/10.1002/admi.202100624
Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.
Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.
The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.
Recommended Articles
Abstract
Figure 1
Figure 1. Predicted energetically low interface structures: IFpristine of the LCO(104)/LNO(11̅0) interface (a) and IFpristine (b) and IFNb–P (c) of the LNO(11̅0)/LPS(010) interface. The insets show the enlarged local geometries of the interface structures. The corresponding interface formation energies are listed in Table 1. The green, red, brown, blue, pink, and yellow balls represent the Li, O, Nb, Co, P, and S ions, respectively.
Figure 2
Figure 3
Figure 3. (Left panels) Calculated layer-decomposed PDOSs for IFpristine of the LCO(104)/LNO(11̅0) interface (a) and IFpristine (b) and IFNb–P (c) of the LNO(11̅0)/LPS(010) interface. The dashed line in each panel indicates the Fermi level. (Right panels) Corresponding layers in the interface models.
Figure 4
Figure 4. Schematic illustrations of ηLi (green line), ηLi+ (black line) and ηe– (red line) in the cathode and SE bulks (a) and in the interface model (b) in ASSBs. Especially in the interface model, the electrons are redistributed at the interface, varying ηLi+ and ηe–. The calculations of Li vacancy formation energy with respect to the Li metal in the bulks and interface model are illustrated in (a,b) as well.
Figure 5
Figure 5. Calculated ηLi(interf) in the LCO(104)/LPS(010) (a,b), LCO(104)/LNO(11̅0) (c), and LNO(11̅0)/LPS(010) (d,e) interface models. In each figure, the black dots represent the directly calculated values shown in Figure 2. The solid lines refer to the values evaluated from eq 7. For comparison, the ηLi(bulk) is also plotted using dashed lines.
References
This article references 47 other publications.
- 1Famprikis, T.; Canepa, P.; Dawson, J. A.; Islam, M. S.; Masquelier, C. Fundamentals of Inorganic Solid-State Electrolytes for Batteries. Nat. Mater. 2019, 18, 1278– 1291, DOI: 10.1038/s41563-019-0431-31Fundamentals of inorganic solid-state electrolytes for batteriesFamprikis, Theodosios; Canepa, Pieremanuele; Dawson, James A.; Islam, M. Saiful; Masquelier, ChristianNature Materials (2019), 18 (12), 1278-1291CODEN: NMAACR; ISSN:1476-1122. (Nature Research)A review. In the crit. area of sustainable energy storage, solid-state batteries have attracted considerable attention due to their potential safety, energy-d. and cycle-life benefits. This Review describes recent progress in the fundamental understanding of inorg. solid electrolytes, which lie at the heart of the solid-state battery concept, by addressing key issues in the areas of multiscale ion transport, electrochem. and mech. properties, and current processing routes. The main electrolyte-related challenges for practical solid-state devices include utilization of metal anodes, stabilization of interfaces and the maintenance of phys. contact, the solns. to which hinge on gaining greater knowledge of the underlying properties of solid electrolyte materials.
- 2Tian, Y.; Shi, T.; Richards, W. D.; Li, J.; Kim, J. C.; Bo, S.-H.; Ceder, G. Compatibility Issues between Electrodes and Electrolytes in Solid-State Batteries. Energy Environ. Sci. 2017, 10, 1150– 1166, DOI: 10.1039/C7EE00534B2Compatibility issues between electrodes and electrolytes in solid-state batteriesTian, Yaosen; Shi, Tan; Richards, William D.; Li, Juchuan; Kim, Jae Chul; Bo, Shou-Hang; Ceder, GerbrandEnergy & Environmental Science (2017), 10 (5), 1150-1166CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)Remarkable success has been achieved in the discovery of ceramic alkali superionic conductors as electrolytes in solid-state batteries; however, obtaining a stable interface between these electrolytes and electrodes is difficult. Only limited studies on the compatibility between electrodes and solid electrolytes have been reported, partially because of the need for expensive instrumentation and special cell designs. Without simple yet powerful tools, these compatibility issues cannot be systematically investigated, thus hindering the generalization of design rules for the integration of solid-state battery components. Herein, we present a methodol. that combines d. functional theory calcns. and simple exptl. techniques such as X-ray diffraction, simultaneous differential scanning calorimetry and thermal gravimetric anal., and electrochem. to efficiently screen the compatibility of numerous electrode/electrolyte pairs. We systemically distinguish between the electrochem. stability of the solid-state conductor, which is relevant wherever the electrolyte contacts an electron pathway, and the electrochem. stability of the electrode/electrolyte interfaces. For the solid electrolyte, we are able to computationally derive an abs. thermodn. stability voltage window, which is small for Na3PS4 and Na3PSe4, and a larger voltage window which can be kinetically stabilized. The exptl. stability, when measured with reliable techniques, falls between these thermodn. and kinetic limits. Employing a Na solid-state system as an example, we demonstrate the efficiency of our method by finding the most stable system (NaCrO2|Na3PS4|Na-Sn) within a selected chem. space (more than 20 different combinations of electrodes and electrolytes). Important selection criteria for the cathode, electrolyte, and anode in solid-state batteries are also derived from this study. The current method not only provides an essential guide for integrating all-solid-state battery components but can also significantly accelerate the expansion of the electrolyte/electrode compatibility data.
- 3Manthiram, A.; Yu, X.; Wang, S. Lithium Battery Chemistries Enabled by Solid-State Electrolytes. Nat. Rev. Mater. 2017, 2, 16103, DOI: 10.1038/natrevmats.2016.1033Lithium battery chemistries enabled by solid-state electrolytesManthiram, Arumugam; Yu, Xingwen; Wang, ShaofeiNature Reviews Materials (2017), 2 (3), 16103CODEN: NRMADL; ISSN:2058-8437. (Nature Publishing Group)Solid-state electrolytes are attracting increasing interest for electrochem. energy storage technologies. In this Review, we provide a background overview and discuss the state of the art, ion-transport mechanisms and fundamental properties of solid-state electrolyte materials of interest for energy storage applications. We focus on recent advances in various classes of battery chemistries and systems that are enabled by solid electrolytes, including all-solid-state lithium-ion batteries and emerging solid-electrolyte lithium batteries that feature cathodes with liq. or gaseous active materials (for example, lithium-air, lithium-sulfur and lithium-bromine systems). A low-cost, safe, aq. electrochem. energy storage concept with a 'mediator-ion' solid electrolyte is also discussed. Advanced battery systems based on solid electrolytes would revitalize the rechargeable battery field because of their safety, excellent stability, long cycle lives and low cost. However, great effort will be needed to implement solid-electrolyte batteries as viable energy storage systems. In this context, we discuss the main issues that must be addressed, such as achieving acceptable ionic cond., electrochem. stability and mech. properties of the solid electrolytes, as well as a compatible electrolyte/electrode interface.
- 4Wang, Y.; Richards, W. D.; Ong, S. P.; Miara, L. J.; Kim, J. C.; Mo, Y.; Ceder, G. Design Principles for Solid-State Lithium Superionic Conductors. Nat. Mater. 2015, 14, 1026– 1031, DOI: 10.1038/nmat43694Design principles for solid-state lithium superionic conductorsWang, Yan; Richards, William Davidson; Ong, Shyue Ping; Miara, Lincoln J.; Kim, Jae Chul; Mo, Yifei; Ceder, GerbrandNature Materials (2015), 14 (10), 1026-1031CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)Lithium solid electrolytes can potentially address two key limitations of the org. electrolytes used in today's lithium-ion batteries, namely, their flammability and limited electrochem. stability. However, achieving a Li+ cond. in the solid state comparable to existing liq. electrolytes (>1 mS cm-1) is particularly challenging. In this work, we reveal a fundamental relationship between anion packing and ionic transport in fast Li-conducting materials and expose the desirable structural attributes of good Li-ion conductors. We find that an underlying body-centered cubic-like anion framework, which allows direct Li hops between adjacent tetrahedral sites, is most desirable for achieving high ionic cond., and that indeed this anion arrangement is present in several known fast Li-conducting materials and other fast ion conductors. These findings provide important insight towards the understanding of ionic transport in Li-ion conductors and serve as design principles for future discovery and design of improved electrolytes for Li-ion batteries.
- 5Kamaya, N.; Homma, K.; Yamakawa, Y.; Hirayama, M.; Kanno, R.; Yonemura, M.; Kamiyama, T.; Kato, Y.; Hama, S.; Kawamoto, K.; Mitsui, A. A Lithium Superionic Conductor. Nat. Mater. 2011, 10, 682– 686, DOI: 10.1038/nmat30665A lithium superionic conductorKamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro; Hirayama, Masaaki; Kanno, Ryoji; Yonemura, Masao; Kamiyama, Takashi; Kato, Yuki; Hama, Shigenori; Kawamoto, Koji; Mitsui, AkioNature Materials (2011), 10 (9), 682-686CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)Batteries are a key technol. in modern society. They are used to power elec. and hybrid elec. vehicles and to store wind and solar energy in smart grids. Electrochem. devices with high energy and power densities can currently be powered only by batteries with org. liq. electrolytes. However, such batteries require relatively stringent safety precautions, making large-scale systems complicated and expensive. The application of solid electrolytes is currently limited because they attain practically useful conductivities (10-2 S/cm) only at 50-80°, which is one order of magnitude lower than those of org. liq. electrolytes. Here, the authors report a Li superionic conductor, Li10GeP2S12 that has a new 3-dimensional framework structure. It exhibits an extremely high Li ionic cond. of 12 mS/cm at room temp. This represents the highest cond. achieved in a solid electrolyte, exceeding even those of liq. org. electrolytes. This new solid-state battery electrolyte has many advantages in terms of device fabrication (facile shaping, patterning and integration), stability (non-volatile), safety (non-explosive) and excellent electrochem. properties (high cond. and wide potential window).
- 6Kato, Y.; Hori, S.; Saito, T.; Suzuki, K.; Hirayama, M.; Mitsui, A.; Yonemura, M.; Iba, H.; Kanno, R. High-Power All-Solid-State Batteries Using Sulfide Superionic Conductors. Nat. Energy 2016, 1, 16030, DOI: 10.1038/nenergy.2016.306High-power all-solid-state batteries using sulfide superionic conductorsKato, Yuki; Hori, Satoshi; Saito, Toshiya; Suzuki, Kota; Hirayama, Masaaki; Mitsui, Akio; Yonemura, Masao; Iba, Hideki; Kanno, RyojiNature Energy (2016), 1 (4), 16030CODEN: NEANFD; ISSN:2058-7546. (Nature Publishing Group)Compared with Li-ion batteries with liq. electrolytes, all-solid-state batteries offer an attractive option owing to their potential in improving the safety and achieving both high power and high energy densities. Despite extensive research efforts, the development of all-solid-state batteries still falls short of expectation largely because of the lack of suitable candidate materials for the electrolyte required for practical applications. Here the authors report Li superionic conductors with an exceptionally high cond. (25 mS cm-1 for Li9.54Si1.74P1.44S11.7Cl0.3), as well as high stability ( ∼0 V vs. Li metal for Li9.6P3S12). A fabricated all-solid-state cell based on this Li conductor has very small internal resistance, esp. at 100 oC. The cell possesses high specific power that is superior to that of conventional cells with liq. electrolytes. Stable cycling with a high c.d. of 18 C (charging/discharging in just 3 min; where C is the C-rate) is also demonstrated.
- 7Murugan, R.; Thangadurai, V.; Weppner, W. Fast Lithium Ion Conduction in Garnet-Type Li7La3Zr2O12. Angew. Chem., Int. Ed. 2007, 46, 7778– 7781, DOI: 10.1002/anie.2007011447Fast lithium ion conduction in garnet-type Li7La3Zr2O12Murugan, Ramaswamy; Thangadurai, Venkataraman; Weppner, WernerAngewandte Chemie, International Edition (2007), 46 (41), 7778-7781CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)Low activation energy and fast Li ion conduction were obsd. for the new compd., Li7La3Zr2O12. Relative to previously reported Li garnets, this solid electrolyte shows a larger cubic lattice const., higher Li ion concn., lower degree of chem. interaction between the Li+ and the other lattice constituents, and higher densification.
- 8Liu, Z.; Fu, W.; Payzant, E. A.; Yu, X.; Wu, Z.; Dudney, N. J.; Kiggans, J.; Hong, K.; Rondinone, A. J.; Liang, C. Anomalous High Ionic Conductivity of Nanoporous β-Li3PS4. J. Am. Chem. Soc. 2013, 135, 975– 978, DOI: 10.1021/ja31108958Anomalous High Ionic Conductivity of Nanoporous β-Li3PS4Liu, Zengcai; Fu, Wujun; Payzant, E. Andrew; Yu, Xiang; Wu, Zili; Dudney, Nancy J.; Kiggans, Jim; Hong, Kunlun; Rondinone, Adam J.; Liang, ChengduJournal of the American Chemical Society (2013), 135 (3), 975-978CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Lithium-ion-conducting solid electrolytes hold promise for enabling high-energy battery chemistries and circumventing safety issues of conventional lithium batteries. Achieving the combination of high ionic cond. and a broad electrochem. window in solid electrolytes is a grand challenge for the synthesis of battery materials. Herein we show an enhancement of the room-temp. lithium-ion cond. by 3 orders of magnitude through the creation of nanostructured Li3PS4. This material has a wide electrochem. window (5 V) and superior chem. stability against lithium metal. The nanoporous structure of Li3PS4 reconciles two vital effects that enhance the ionic cond.: (a) the redn. of the dimensions to a nanometer-sized framework stabilizes the high-conduction β phase that occurs at elevated temps., and (b) the high surface-to-bulk ratio of nanoporous β-Li3PS4 promotes surface conduction. Manipulating the ionic cond. of solid electrolytes has far-reaching implications for materials design and synthesis in a broad range of applications, including batteries, fuel cells, sensors, photovoltaic systems, and so forth.
- 9Du, M.; Liao, K.; Lu, Q.; Shao, Z. Recent Advances in the Interface Engineering of Solid-State Li-Ion Batteries with Artificial Buffer Layers: Challenges, Materials, Construction, and Characterization. Energy Environ. Sci. 2019, 12, 1780– 1804, DOI: 10.1039/C9EE00515C9Recent advances in the interface engineering of solid-state Li-ion batteries with artificial buffer layers: challenges, materials, construction, and characterizationDu, Mingjie; Liao, Kaiming; Lu, Qian; Shao, ZongpingEnergy & Environmental Science (2019), 12 (6), 1780-1804CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)A review. Although solid-state Li-ion batteries (SSBs) provide opportunities to simplify safety measures (e.g., sophisticated thermal management systems, overpressure vents, charge interruption devices) currently used in conventional Li-ion batteries (LIBs) with flammable org. liq. electrolytes, the poor interface compatibility (both phys. and chem.) between the electrode materials and solid electrolyte strongly hinders the practical application of SSBs. The fabrication of artificial buffer layers (ABLs) was therefore proposed, and it has been an effective approach for overcoming the interface issues of SSBs. In this review paper, we provide a comprehensive summary of recent progress in interface engineering and advanced techniques for characterization of such interfaces in SSBs. First, the crit. issues and challenges facing SSBs assocd. with the stability of the cathode/solid electrolyte and anode/solid electrolyte interfaces are discussed. The latest research approaches and synthetic strategies to improve the performance of SSBs that rely on interface engineering with ABLs are extensively reviewed. The characterization strategies for in situ and ex situ interfacial observation and anal. are comprehensively summarized. Finally, the crit. issues assocd. with electrode-electrolyte interfaces are emphasized, and perspectives regarding the development of high-quality buffer layers are presented.
- 10Auvergniot, J.; Cassel, A.; Ledeuil, J.-B.; Viallet, V.; Seznec, V.; Dedryvère, R. Interface Stability of Argyrodite Li6PS5Cl toward LiCoO2, LiNi1/3Co1/3Mn1/3O2, and LiMn2O4 in Bulk All-Solid-State Batteries. Chem. Mater. 2017, 29, 3883– 3890, DOI: 10.1021/acs.chemmater.6b0499010Interface Stability of Argyrodite Li6PS5Cl toward LiCoO2, LiNi1/3Co1/3Mn1/3O2, and LiMn2O4 in Bulk All-Solid-State BatteriesAuvergniot, Jeremie; Cassel, Alice; Ledeuil, Jean-Bernard; Viallet, Virginie; Seznec, Vincent; Dedryvere, RemiChemistry of Materials (2017), 29 (9), 3883-3890CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Argyrodite Li6PS5Cl is a good candidate for being a solid electrolyte for bulk all-solid-state Li-ion batteries because of its high ionic cond. and its good processability. However, the interface stability of sulfide-based electrolytes toward active materials (neg. or pos. electrodes) is known to be lower than that of oxide-based electrolytes. In this work, we investigate the interface stability of argyrodite toward several pos. electrode materials: LiCoO2, LiNi1/3Co1/3Mn1/3O2, and LiMn2O4. All-solid-state half-cells were cycled, and the interface mechanisms were characterized by Auger electron spectroscopy and XPS. We show that Li6PS5Cl is oxidized into elemental sulfur, lithium polysulfides, P2Sx (x ≥ 5), phosphates, and LiCl at the interface with the pos. electrode active materials. In spite of this interface reactivity, good capacity retention was obsd. over 300 cycles. Li6PS5Cl shows some reversible electrochem. activity (redox processes) that might contribute to the reversible capacity of the battery.
- 11Dai, J.; Yang, C.; Wang, C.; Pastel, G.; Hu, L. Interface Engineering for Garnet-Based Solid-State Lithium-Metal Batteries: Materials, Structures, and Characterization. Adv. Mater. 2018, 30, 1802068, DOI: 10.1002/adma.201802068There is no corresponding record for this reference.
- 12Han, X.; Gong, Y.; Fu, K.; He, X.; Hitz, G. T.; Dai, J.; Pearse, A.; Liu, B.; Wang, H.; Rubloff, G.; Mo, Y.; Thangadurai, V.; Wachsman, E. D.; Hu, L. Negating Interfacial Impedance in Garnet-Based Solid-State Li Metal Batteries. Nat. Mater. 2017, 16, 572– 579, DOI: 10.1038/nmat482112Negating interfacial impedance in garnet-based solid-state Li metal batteriesHan, Xiaogang; Gong, Yunhui; Fu, Kun; He, Xingfeng; Hitz, Gregory T.; Dai, Jiaqi; Pearse, Alex; Liu, Boyang; Wang, Howard; Rubloff, Gary; Mo, Yifei; Thangadurai, Venkataraman; Wachsman, Eric D.; Hu, LiangbingNature Materials (2017), 16 (5), 572-579CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)Garnet-type solid-state electrolytes have attracted extensive attention due to their high ionic cond., approaching 1 mS cm-1, excellent environmental stability, and wide electrochem. stability window, from lithium metal to ∼6 V. However, to date, there has been little success in the development of high-performance solid-state batteries using these exceptional materials, the major challenge being the high solid-solid interfacial impedance between the garnet electrolyte and electrode materials. In this work, we effectively address the large interfacial impedance between a lithium metal anode and the garnet electrolyte using ultrathin aluminum oxide (Al2O3) by at. layer deposition. Li7La2.75Ca0.25Zr1.75Nb0.25O12 (LLCZN) is the garnet compn. of choice in this work due to its reduced sintering temp. and increased lithium ion cond. A significant decrease of interfacial impedance, from 1,710 Ω cm2 to 1 Ω cm2, was obsd. at room temp., effectively negating the lithium metal/garnet interfacial impedance. Exptl. and computational results reveal that the oxide coating enables wetting of metallic lithium in contact with the garnet electrolyte surface and the lithiated-alumina interface allows effective lithium ion transport between the lithium metal anode and garnet electrolyte. We also demonstrate a working cell with a lithium metal anode, garnet electrolyte and a high-voltage cathode by applying the newly developed interface chem.
- 13Ahmad, Z.; Viswanathan, V. Stability of Electrodeposition at Solid-Solid Interfaces and Implications for Metal Anodes. Phys. Rev. Lett. 2017, 119, 056003, DOI: 10.1103/PhysRevLett.119.05600313Stability of electrodeposition at solid-solid interfaces and implications for metal anodesAhmad, Zeeshan; Viswanathan, VenkatasubramanianPhysical Review Letters (2017), 119 (5), 056003/1-056003/6CODEN: PRLTAO; ISSN:1079-7114. (American Physical Society)We generalize the conditions for stable electrodeposition at isotropic solid-solid interfaces using a kinetic model which incorporates the effects of stresses and surface tension at the interface. We develop a stability diagram that shows two regimes of stability: a previously known pressure-driven mechanism and a new d.-driven stability mechanism that is governed by the relative d. of metal in the two phases. We show that inorg. solids and solid polymers generally do not lead to stable electrodeposition, and provide design guidelines for achieving stable electrodeposition.
- 14Gao, B.; Jalem, R.; Ma, Y.; Tateyama, Y. Li+ Transport Mechanism at the Heterogeneous Cathode/Solid Electrolyte Interface in an All-Solid-State Battery via the First-Principles Structure Prediction Scheme. Chem. Mater. 2020, 32, 85– 96, DOI: 10.1021/acs.chemmater.9b0231114Li+ Transport Mechanism at the Heterogeneous Cathode/Solid Electrolyte Interface in an All-Solid-State Battery via the First-Principles Structure Prediction SchemeGao, Bo; Jalem, Randy; Ma, Yanming; Tateyama, YoshitakaChemistry of Materials (2020), 32 (1), 85-96CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)High interfacial resistance between a cathode and solid electrolyte (SE) has been a long-standing problem for all-solid-state batteries (ASSBs). Though thermodn. approaches suggested possible phase transformations at the interfaces, direct analyses of the ionic and electronic states at the solid/solid interfaces are still crucial. Here, newly constructed scheme is used for predicting heterogeneous interface structures via the swarm-intelligence-based crystal structure anal. by particle swarm optimization method, combined with d. functional theory calcns., and systematically investigated the mechanism of Li-ion (Li+) transport at the interface in LiCoO2 cathode/β-Li3PS4 SE, a representative ASSB system. The sampled favorable interface structures indicate that the interfacial reaction layer is formed with both mixing of Co and P cations and mixing of O and S anions. The calcd. site-dependent Li chem. potentials μLi(r) and potential energy surfaces for Li+ migration across the interfaces reveal that interfacial Li+ sites with higher μLi(r) values cause dynamic Li+ depletion with the interfacial electron transfer in the initial stage of charging. The Li+-depleted space can allow oxidative decompn. of SE materials. These pieces of evidence theor. confirm the primary origin of the obsd. interfacial resistance in ASSBs and the mechanism of the resistance decrease obsd. with oxide buffer layers (e.g., LiNbO3) and oxide SE. The present study also provides a perspective for the structure sampling of disordered heterogeneous solid/solid interfaces on the at. scale.
- 15Takada, K. Progress and Prospective of Solid-State Lithium Batteries. Acta Mater. 2013, 61, 759– 770, DOI: 10.1016/j.actamat.2012.10.03415Progress and prospective of solid-state lithium batteriesTakada, KazunoriActa Materialia (2013), 61 (3), 759-770CODEN: ACMAFD; ISSN:1359-6454. (Elsevier Ltd.)A review. The development of lithium-ion batteries has energized studies of solid-state batteries, because the non-flammability of their solid electrolytes offers a fundamental soln. to safety concerns. Since poor ionic conduction in solid electrolytes is a major drawback in solid-state batteries, such studies were focused on the enhancement of ionic cond. The studies have identified some high performance solid electrolytes; however, some disadvantages have remained hidden until their use in batteries. This paper reviews the development of solid electrolytes and their application to solid-state lithium batteries.
- 16Takada, K.; Ohta, N.; Zhang, L.; Fukuda, K.; Sakaguchi, I.; Ma, R.; Osada, M.; Sasaki, T. Interfacial Modification for High-Power Solid-State Lithium Batteries. Solid State Ionics 2008, 179, 1333– 1337, DOI: 10.1016/j.ssi.2008.02.01716Interfacial modification for high-power solid-state lithium batteriesTakada, Kazunori; Ohta, Narumi; Zhang, Lianqi; Fukuda, Katsutoshi; Sakaguchi, Isao; Ma, Renzhi; Osada, Minoru; Sasaki, TakayoshiSolid State Ionics (2008), 179 (27-32), 1333-1337CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)Interfaces between LiCoO2 and sulfide solid electrolytes were modified in order to enhance the high-rate capability of solid-state lithium batteries. Thin films of oxide solid electrolytes, Li4Ti5O12, LiNbO3, and LiTaO3, were interposed at the interfaces as buffer layers. Changes in the high-rate performance upon heat treatment revealed that the buffer layer should be formed at low temp. to avoid thermal diffusion of the elements. Buffer layers of LiNbO3 and LiTaO3 can be formed at low temp. for the interfacial modification, because they show high ionic conduction in their amorphous states, and so are more effective than Li4Ti5O12 for high-power densities.
- 17Haruyama, J.; Sodeyama, K.; Han, L.; Takada, K.; Tateyama, Y. Space–Charge Layer Effect at Interface between Oxide Cathode and Sulfide Electrolyte in All-Solid-State Lithium-Ion Battery. Chem. Mater. 2014, 26, 4248– 4255, DOI: 10.1021/cm501695917Space-Charge Layer Effect at Interface between Oxide Cathode and Sulfide Electrolyte in All-Solid-State Lithium-Ion BatteryHaruyama, Jun; Sodeyama, Keitaro; Han, Liyuan; Takada, Kazunori; Tateyama, YoshitakaChemistry of Materials (2014), 26 (14), 4248-4255CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)The authors theor. elucidated the characteristics of the space-charge layer (SCL) at interfaces between oxide cathode and sulfide electrolyte in all-solid-state Li-ion batteries (ASS-LIBs) and the effect of the buffer layer interposition, for the 1st time, via the calcns. with d. functional theory (DFT) + U framework. As a most representative system, the authors examd. the interfaces between LiCoO2 cathode and β-Li3PS4 solid electrolyte (LCO/LPS), and the LiCoO2/LiNbO3/β-Li3PS4 (LCO/LNO/LPS) interfaces with the LiNbO3 buffer layers. The DFT+U calcns., coupling with a systematic procedure for interface matching, showed the stable structures and the electronic states of the interfaces. The LCO/LPS interface has attractive Li adsorption sites and rather disordered structure, whereas the interposition of the LNO buffer layers forms smooth interfaces without Li adsorption sites for both LCO and LPS sides. The calcd. energies of the Li-vacancy formation and the Li migration reveal that subsurface Li in the LPS side can begin to transfer at the under-voltage condition in the LCO/LPS interface, which suggests the SCL growth at the beginning of charging, leading to the interfacial resistance. The LNO interposition suppresses this growth of SCL and provides smooth Li transport paths free from the possible bottlenecks. These aspects on the at. scale will give a useful perspective for the further improvement of the ASS-LIB performance.
- 18Sakuda, A.; Hayashi, A.; Tatsumisago, M. Interfacial Observation between LiCoO2 Electrode and Li2S–P2S5 Solid Electrolytes of All-Solid-State Lithium Secondary Batteries Using Transmission Electron Microscopy. Chem. Mater. 2010, 22, 949– 956, DOI: 10.1021/cm901819c18Interfacial Observation between LiCoO2 Electrode and Li2S-P2S5 Solid Electrolytes of All-Solid-State Lithium Secondary Batteries using Transmission Electron MicroscopySakuda, Atsushi; Hayashi, Akitoshi; Tatsumisago, MasahiroChemistry of Materials (2010), 22 (3), 949-956CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)In all-solid-state lithium secondary batteries, both the electrode and electrolyte materials are solid. The electrode and solid electrolyte interface structure and morphol. affect a battery electrochem. performance. Observation of the interface between LiCoO2 cathode and highly lithium-ion-conducting Li2S-P2S5 solid electrolyte was conducted using transmission electron microscopy. An interfacial layer was formed at the interface between LiCoO2 electrode and Li2S-P2S5 solid electrolyte after the battery initial charge. Furthermore, mutual diffusions of Co, P, and S at the interface between LiCoO2 and Li2S-P2S5 were obsd. The mutual diffusion and the formation of the interfacial layer were suppressed using LiCoO2 particles coated with Li2SiO3 thin film. Results showed that all-solid-state batteries using Li2SiO3-coated LiCoO2 had better electrochem. performance than those using non-coated LiCoO2. The all-solid-state batteries functioned at -30°. Moreover, the all-solid-state battery using Li2SiO3-coated LiCoO2 was charged and discharged under a high c.d. of 40 mA/cm2 at 100°.
- 19Koerver, R.; Zhang, W.; de Biasi, L.; Schweidler, S.; Kondrakov, A. O.; Kolling, S.; Brezesinski, T.; Hartmann, P.; Zeier, G. W.; Janek, J. Chemo-Mechanical Expansion of Lithium Electrode Materials—on the Route to Mechanically Optimized All-Solid-State Batteries. Energy Environ. Sci. 2018, 11, 2142– 2158, DOI: 10.1039/C8EE00907D19Chemo-mechanical expansion of lithium electrode materials - on the route to mechanically optimized all-solid-state batteriesKoerver, Raimund; Zhang, Wenbo; de Biasi, Lea; Schweidler, Simon; Kondrakov, Aleksandr O.; Kolling, Stefan; Brezesinski, Torsten; Hartmann, Pascal; Zeier, Wolfgang G.; Janek, JuergenEnergy & Environmental Science (2018), 11 (8), 2142-2158CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)Charge and discharge of lithium ion battery electrodes is accompanied by severe vol. changes. In a confined space, the vol. cannot expand, leading to significant pressures induced by local microstructural changes within the battery. While vol. changes appear to be less crit. in batteries with liq. electrolytes, they will be more crit. in the case of lithium ion batteries with solid electrolytes and they will be even more crit. and detrimental in the case of all-solid-state batteries with a lithium metal electrode. In this work we first summarize, compare, and analyze the vol. changes occurring in state of the art electrode materials, based on crystallog. studies. A quant. anal. follows that is based on the evaluation of the partial molar volume of lithium as a function of the degree of lithiation for different electrode materials. Second, the reaction vols. of operating full cells ("charge/discharge vols.") are exptl. detd. from pressure-dependent open-circuit voltage measurements. The resulting changes in the open-circuit voltage are in the order of 1 mV/100 MPa, are well measurable, and agree with changes obsd. in the crystallog. data. Third, the pressure changes within solid-state batteries are approximated under the assumption of incompressibility, i.e. for const. vol. of the cell casing, and are compared to exptl. data obtained from model-type full cells. In addn. to the understanding of the occurring vol. changes of electrode materials and resulting pressure changes in solid-state batteries, we propose "mech." blending of electrode materials to achieve better cycling performance when aiming at "zero-strain" electrodes.
- 20Koerver, R.; Aygün, I.; Leichtweiß, T.; Dietrich, C.; Zhang, W.; Binder, J. O.; Hartmann, P.; Zeier, W. G.; Janek, J. Capacity Fade in Solid-State Batteries: Interphase Formation and Chemomechanical Processes in Nickel-Rich Layered Oxide Cathodes and Lithium Thiophosphate Solid Electrolytes. Chem. Mater. 2017, 29, 5574– 5582, DOI: 10.1021/acs.chemmater.7b0093120Capacity Fade in Solid-State Batteries: Interphase Formation and Chemomechanical Processes in Nickel-Rich Layered Oxide Cathodes and Lithium Thiophosphate Solid ElectrolytesKoerver, Raimund; Ayguen, Isabel; Leichtweiss, Thomas; Dietrich, Christian; Zhang, Wenbo; Binder, Jan O.; Hartmann, Pascal; Zeier, Wolfgang G.; Janek, JuergenChemistry of Materials (2017), 29 (13), 5574-5582CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)All-solid-state lithium ion batteries may become long-term, stable, high-performance energy storage systems for the next generation of elec. vehicles and consumer electronics, depending on the compatibility of electrode materials and suitable solid electrolytes. Nickel-rich layered oxides are nowadays the benchmark cathode materials for conventional lithium ion batteries because of their high storage capacity and the resulting high energy d., and their use in solid-state systems is the next necessary step. In this study, we present the successful implementation of a Li[Ni,Co,Mn]O2 material with high nickel content (LiNi0.8Co0.1Mn0.1O2, NCM-811) in a bulk-type solid-state battery with β-Li3PS4 as a sulfide-based solid electrolyte. We investigate the interface behavior at the cathode and demonstrate the important role of the interface between the active materials and the solid electrolyte for the battery performance. A passivating cathode/electrolyte interphase layer forms upon charging and leads to an irreversible first cycle capacity loss, corresponding to a decompn. of the sulfide electrolyte. In situ electrochem. impedance spectroscopy and X-ray photoemission spectroscopy are used to monitor this formation. We demonstrate that most of the interphase formation takes place in the first cycle, when charging to potentials above 3.8 V vs Li+/Li. The resulting overvoltage of the passivating layer is a detrimental factor for capacity retention. In addn. to the interfacial decompn., the chemomech. contraction of the active material upon delithiation causes contact loss between the solid electrolyte and active material particles, further increasing the interfacial resistance and capacity loss. These results highlight the crit. role of (electro-)chemo-mech. effects in solid-state batteries.
- 21Swift, M. W.; Qi, Y. First-Principles Prediction of Potentials and Space-Charge Layers in All-Solid-State Batteries. Phys. Rev. Lett. 2019, 122, 167701, DOI: 10.1103/PhysRevLett.122.16770121First-Principles Prediction of Potentials and Space-Charge Layers in All-Solid-State BatteriesSwift, Michael W.; Qi, YuePhysical Review Letters (2019), 122 (16), 167701pp.CODEN: PRLTAO; ISSN:1079-7114. (American Physical Society)As all-solid-state batteries (SSBs) develop as an alternative to traditional cells, a thorough theor. understanding of driving forces behind battery operation is needed. We present a fully first-principles-informed model of potential profiles in SSBs and apply the model to the Li/LiPON/LixCoO2 system. The model predicts interfacial potential drops driven by both electron transfer and Li+ space-charge layers that vary with the SSB's state of charge. The results suggest a lower electronic ionization potential in the solid electrolyte favors Li+ transport, leading to higher discharge power.
- 22Nomura, Y.; Yamamoto, K.; Hirayama, T.; Ouchi, S.; Igaki, E.; Saitoh, K. Direct Observation of a Li-Ionic Space-Charge Layer Formed at an Electrode/Solid-Electrolyte Interface. Angew. Chem. 2019, 131, 5346– 5350, DOI: 10.1002/ange.201814669There is no corresponding record for this reference.
- 23Tian, H.-K.; Qi, Y. Simulation of the Effect of Contact Area Loss in All-Solid-State Li-Ion Batteries. J. Electrochem. Soc. 2017, 164, E3512– E3521, DOI: 10.1149/2.0481711jes23Simulation of the Effect of Contact Area Loss in All-Solid-State Li-Ion BatteriesTian, Hong-Kang; Qi, YueJournal of the Electrochemical Society (2017), 164 (11), E3512-E3521CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)Maintaining the phys. contact between the solid electrolyte and the electrode is important to improve the performance of all-solid-state batteries. Imperfect contact can be formed during cell fabrication and will be worsened due to cycling, resulting in degrdn. of the battery performance. In this paper, the effect of imperfect contact area was incorporated into a 1-D Newman battery model by assuming the current and Li concn. will be localized at the contacted area. Const. current discharging processes at different rates and contact areas were simulated for a film-type Li/LiPON/LiCoO2 all-solid-state Li-ion battery. The capacity drop was correlated with the contact area loss. It was found at lower cutoff voltage, the correlation is almost linear with a slope of 1; while at a higher cutoff voltage, the dropping rate is slower. To establish the relationship between the applied pressure and the contact area, Persson's contact mechanics theory was applied, as it uses self-affined surfaces to simplify the multi-length scale contacts in all-solid-state batteries. The contact area and pressure were computed for both film-type and bulk-type all-solid-state Li-ion batteries. The model is then used to suggest how much pressures should be applied to recover the capacity drop due to contact area loss.
- 24Aguesse, F.; Manalastas, W.; Buannic, L.; Lopez del Amo, J. M.; Singh, G.; Llordés, A.; Kilner, J. Investigating the Dendritic Growth during Full Cell Cycling of Garnet Electrolyte in Direct Contact with Li Metal. ACS Appl. Mater. Interfaces 2017, 9, 3808– 3816, DOI: 10.1021/acsami.6b1392524Investigating the Dendritic Growth during Full Cell Cycling of Garnet Electrolyte in Direct Contact with Li MetalAguesse, Frederic; Manalastas, William; Buannic, Lucienne; Lopez del Amo, Juan Miguel; Singh, Gurpreet; Llordes, Anna; Kilner, JohnACS Applied Materials & Interfaces (2017), 9 (4), 3808-3816CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)All-solid-state batteries including a garnet ceramic as electrolyte are potential candidates to replace the currently used Li-ion technol., as they offer safer operation and higher energy storage performances. However, the development of ceramic electrolyte batteries faces several challenges at the electrode/electrolyte interfaces, which need to withstand high current densities to enable competing C-rates. The authors study the limits of the anode/electrolyte interface in a full cell that includes a Li-metal anode, LiFePO4 cathode, and garnet ceramic electrolyte. The addn. of a liq. interfacial layer between the cathode and the ceramic electrolyte is a prerequisite to achieve low interfacial resistance and to enable full use of the active material contained in the porous electrode. Reproducible and const. discharge capacities are extd. from the cathode active material during the 1st 20 cycles, revealing high efficiency of the garnet as electrolyte and the interfaces, but prolonged cycling leads to abrupt cell failure. By using a combination of structural and chem. characterization techniques, such as SEM and solid-state NMR, as well as electrochem. and impedance spectroscopy, a sudden impedance drop occurs in the cell due to the formation of metallic Li and its propagation within the ceramic electrolyte. This degrdn. process is originated at the interface between the Li-metal anode and the ceramic electrolyte layer and leads to electromech. failure and cell short-circuit. Improvement of the performances is obsd. when cycling the full cell at 55°, as the Li-metal softening favors the interfacial contact. Various degrdn. mechanisms probably explain this behavior.
- 25Krauskopf, T.; Hartmann, H.; Zeier, W. G.; Janek, J. Toward a Fundamental Understanding of the Lithium Metal Anode in Solid-State Batteries—An Electrochemo-Mechanical Study on the Garnet-Type Solid Electrolyte Li6.25Al0.25La3Zr2O12. ACS Appl. Mater. Interfaces 2019, 11, 14463– 14477, DOI: 10.1021/acsami.9b0253725Toward a Fundamental Understanding of the Lithium Metal Anode in Solid-State Batteries-An Electrochemo-Mechanical Study on the Garnet-Type Solid Electrolyte Li6.25Al0.25La3Zr2O12Krauskopf, Thorben; Hartmann, Hannah; Zeier, Wolfgang G.; Janek, JuergenACS Applied Materials & Interfaces (2019), 11 (15), 14463-14477CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)For the development of next-generation lithium batteries, major research effort is made to enable a reversible lithium metal anode by the use of solid electrolytes. However, the fundamentals of the solid-solid interface and esp. the processes that take place under current load are still not well characterized. By measuring pressure-dependent electrode kinetics, we explore the electrochemo-mech. behavior of the lithium metal anode on the garnet electrolyte Li6.25Al0.25La3Zr2O12. Because of the stability against redn. in contact with the lithium metal, this serves as an optimal model system for kinetic studies without electrolyte degrdn. We show that the interfacial resistance becomes negligibly small and converges to practically 0 Ω·cm2 at high external pressures of several 100 MPa. To the best of our knowledge, this is the smallest reported interfacial resistance in the literature without the need for any interlayer. We interpret this observation by the concept of constriction resistance and show that the contact geometry in combination with the ionic transport in the solid electrolyte dominates the interfacial contributions for a clean interface in equil. Furthermore, we show that-under anodic operating conditions-the vacancy diffusion limitation in the lithium metal restricts the rate capability of the lithium metal anode because of contact loss caused by vacancy accumulation and the resulting pore formation near the interface. Results of a kinetic model show that the interface remains morphol. stable only when the anodic load does not exceed a crit. value of approx. 100 μA·cm-2, which is not high enough for practical cell setups employing a planar geometry. We highlight that future research on lithium metal anodes on solid electrolytes needs to focus on the transport within and the morphol. instability of the metal electrode. Overall, the results help to develop a deeper understanding of the lithium metal anode on solid electrolytes, and the major conclusions are not limited to the Li|Li6.25Al0.25La3Zr2O12 interface.
- 26Zhang, W.; Richter, F. H.; Culver, S. P.; Leichtweiss, T.; Lozano, J. G.; Dietrich, C.; Bruce, P. G.; Zeier, W. G.; Janek, J. Degradation Mechanisms at the Li10GeP2S12/LiCoO2 Cathode Interface in an All-Solid-State Lithium-Ion Battery. ACS Appl. Mater. Interfaces 2018, 10, 22226– 22236, DOI: 10.1021/acsami.8b0513226Degradation mechanisms at the Li10GeP2S12/LiCoO2 cathode interface in an all-solid-state lithium-ion batteryZhang, Wenbo; Richter, Felix H.; Culver, Sean P.; Leichtweiss, Thomas; Lozano, Juan G.; Dietrich, Christian; Bruce, Peter G.; Zeier, Wolfgang G.; Janek, JuergenACS Applied Materials & Interfaces (2018), 10 (26), 22226-22236CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)All-solid-state batteries (ASSBs) show great potential for providing high power and energy densities with enhanced battery safety. While new solid electrolytes (SEs) have been developed with high enough ionic conductivities, SSBs with long operational life are still rarely reported. Therefore, on the way to high-performance and long-life ASSBs, a better understanding of the complex degrdn. mechanisms, occurring at the electrode/electrolyte interfaces is pivotal. While the lithium metal/solid electrolyte interface is receiving considerable attention due to the quest for high energy d., the interface between the active material and solid electrolyte particles within the composite cathode is arguably the most difficult to solve and study. In this work, multiple characterization methods are combined to better understand the processes that occur at the LiCoO2 cathode and the Li10GeP2S12 solid electrolyte interface. Indium and Li4Ti5O12 are used as anode materials to avoid the instability problems assocd. with Li-metal anodes. Capacity fading and increased impedances are obsd. during long-term cycling. Postmortem anal. with scanning transmission electron microscopy, electron energy loss spectroscopy, x-ray diffraction, and XPS show that electrochem. driven mech. failure and degrdn. at the cathode/solid electrolyte interface contribute to the increase in internal resistance and the resulting capacity fading. These results suggest that the development of electrochem. more stable SEs and the engineering of cathode/SE interfaces are crucial for achieving reliable SSB performance.
- 27Richards, W. D.; Miara, L. J.; Wang, Y.; Kim, J. C.; Ceder, G. Interface Stability in Solid-State Batteries. Chem. Mater. 2016, 28, 266– 273, DOI: 10.1021/acs.chemmater.5b0408227Interface Stability in Solid-State BatteriesRichards, William D.; Miara, Lincoln J.; Wang, Yan; Kim, Jae Chul; Ceder, GerbrandChemistry of Materials (2016), 28 (1), 266-273CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Development of high cond. solid-state electrolytes for lithium ion batteries has proceeded rapidly in recent years, but incorporating these new materials into high-performing batteries has proven difficult. Interfacial resistance is now the limiting factor in many systems, but the exact mechanisms of this resistance have not been fully explained - in part because exptl. evaluation of the interface can be very difficult. In this work, we develop a computational methodol. to examine the thermodn. of formation of resistive interfacial phases. The predicted interfacial phase formation is well correlated with exptl. interfacial observations and battery performance. We calc. that thiophosphate electrolytes have esp. high reactivity with high voltage cathodes and a narrow electrochem. stability window. We also find that a no. of known electrolytes are not inherently stable but react in situ with the electrode to form passivating but ionically conducting barrier layers. As a ref. for experimentalists, we tabulate the stability and expected decompn. products for a wide range of electrolyte, coating, and electrode materials including a no. of high-performing combinations that have not yet been attempted exptl.
- 28Han, F.; Zhu, Y.; He, X.; Mo, Y.; Wang, C. Electrochemical Stability of Li10GeP2S12 and Li7La3Zr2O12 Solid Electrolytes. Adv. Energy Mater. 2016, 6, 1501590, DOI: 10.1002/aenm.201501590There is no corresponding record for this reference.
- 29Gao, B.; Jalem, R.; Tateyama, Y. Surface-Dependent Stability of the Interface between Garnet Li7La3Zr2O12 and the Li Metal in the All-Solid-State Battery from First-Principles Calculations. ACS Appl. Mater. Interfaces 2020, 12, 16350– 16358, DOI: 10.1021/acsami.9b2301929Surface-Dependent Stability of the Interface between Garnet Li7La3Zr2O12 and the Li Metal in the All-Solid-State Battery from First-Principles CalculationsGao, Bo; Jalem, Randy; Tateyama, YoshitakaACS Applied Materials & Interfaces (2020), 12 (14), 16350-16358CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)The garnet-type Li7La3Zr2O12 (LLZO) solid electrolyte is of particular interest because of its good chem. stability under atm. condition, suitable for practical all-solid-state batteries (ASSBs). However, recent works obsd. electrochem. instability at the LLZO/Li interfaces. Herein, the origin is revealed of the instability by performing a comprehensive first-principles investigation with a high-throughput interface structure search scheme, based on the d. functional theory framework. Based on the constructed phase diagrams of low-index surfaces, it was found that the coordinatively unsatd. (i.e. coordination no. < 6) Zr sites exist widely on the low-energy LLZO surfaces. These undercoordinated Zr sites are reduced once the LLZO surface is in contact with the Li metal, leading to chem. instability of the LLZO/Li interface. Besides, the calcd. formation and adhesion energies of interfaces suggest that the Li wettability on the LLZO surface is dependent on the termination structure. The employment of the approaches such as by controlling the synthesis atm. are needed for preventing the redn. of LLZO against the Li metal. The present anal. with comprehensive first-principles calcns. provides a novel perspective for the rational optimization of the interface between LLZO electrolyte and Li metal anode in the ASSB.
- 30Fingerle, M.; Buchheit, R.; Sicolo, S.; Albe, K.; Hausbrand, R. Reaction and Space Charge Layer Formation at the LiCoO2–LiPON Interface: Insights on Defect Formation and Ion Energy Level Alignment by a Combined Surface Science–Simulation Approach. Chem. Mater. 2017, 29, 7675– 7685, DOI: 10.1021/acs.chemmater.7b0089030Reaction and Space Charge Layer Formation at the LiCoO2-LiPON Interface: Insights on Defect Formation and Ion Energy Level Alignment by a Combined Surface Science-Simulation ApproachFingerle, Mathias; Buchheit, Roman; Sicolo, Sabrina; Albe, Karsten; Hausbrand, ReneChemistry of Materials (2017), 29 (18), 7675-7685CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)In this contribution, we investigate the formation and evolution of LiCoO2-LiPON interfaces upon annealing using photoelectron spectroscopy. We identify interlayer compds. related to the deposition process and study the chem. reactions leading to interlayer formation. Based on the structure of the pristine interface as well as on its evolution upon annealing, we relate reaction layer and space charge layer formation to chem. potential differences between the two materials. The results are discussed in terms of a combined Li-ion and electron interface energy level scheme providing insights into fundamental charge transfer processes. In constructing the energy level alignment, we take into account calcd. defect formation energies of lithium in the cathode and solid electrolyte.
- 31Nakamura, T.; Amezawa, K.; Kulisch, J.; Zeier, W. G.; Janek, J. Guidelines for All-Solid-State Battery Design and Electrode Buffer Layers Based on Chemical Potential Profile Calculation. ACS Appl. Mater. Interfaces 2019, 11, 19968– 19976, DOI: 10.1021/acsami.9b0305331Guidelines for All-Solid-State Battery Design and Electrode Buffer Layers Based on Chemical Potential Profile CalculationNakamura, Takashi; Amezawa, Koji; Kulisch, Jorn; Zeier, Wolfgang G.; Janek, JurgenACS Applied Materials & Interfaces (2019), 11 (22), 19968-19976CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)Protective coatings on cathode active materials have become paramount for the implementation of solid-state batteries; however, the development of coatings lacks the understanding of the necessary coating properties. In this study, guidelines for the design of solid electrolytes and electrode coatings in all-solid-state batteries are proposed from the viewpoint of the steady-state Li chem. potential profile across the battery cell. The model calcn. of the (electro)chem. potential profile in all-solid-state batteries is established by considering the steady-state mixed ionic and electronic conduction in the solid electrolyte under the assumption of local equil. For quant. discussion, the potential profiles within oxygen ion conductors are calcd. instead of Li/Na ion conductors as their partial electronic conductivities have not been reported so far in sufficient detail. Based on the calcd. chem. potential profile, two main conclusions are obtained: the decisive factor for the formation of the chem. potential profile of the neutral mobile component (e.g., oxygen or lithium) in the solid electrolyte is its electronic cond. (and the activity dependence) and a particularly large potential drop is formed in a region where the electronic cond. becomes small. While these conclusions are valid and general for any solid electrolyte device, they are particularly important for the design of protective coatings and the understanding of the functionality of self-assembled solid electrolyte interphases in all-solid-state batteries. To protect the solid electrolyte from decompn. by redn./oxidn. at the anode/cathode interfaces, a sufficient chem. potential drop is necessary within the coating layer or directly at the interphase layer. To achieve this situation, the coating/interphase materials need to have a lower electronic cond. than the solid electrolyte.
- 32Leung, K. DFT Modelling of Explicit Solid–Solid Interfaces in Batteries: Methods and Challenges. Phys. Chem. Chem. Phys. 2020, 22, 10412– 10425, DOI: 10.1039/C9CP06485K32DFT modelling of explicit solid-solid interfaces in batteries: methods and challengesLeung, KevinPhysical Chemistry Chemical Physics (2020), 22 (19), 10412-10425CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)D. Functional Theory (DFT) calcns. of electrode material properties in high energy d. storage devices like lithium batteries have been std. practice for decades. In contrast, DFT modeling of explicit interfaces in batteries arguably lacks universally adopted methodol. and needs further conceptual development. In this paper, we focus on solid-solid interfaces, which are ubiquitous not just in all-solid state batteries; liq.-electrolyte-based batteries often rely on thin, solid passivating films on electrode surfaces to function. We use metal anode calcns. to illustrate that explicit interface models are crit. for elucidating contact potentials, elec. fields at interfaces, and kinetic stability with respect to parasitic reactions. The examples emphasize three key challenges: (1) the "dirty" nature of most battery electrode surfaces; (2) voltage calibration and control; and (3) the fact that interfacial structures are governed by kinetics, not thermodn. To meet these challenges, developing new computational techniques and importing insights from other electrochem. disciplines will be beneficial.
- 33Haruyama, J.; Sodeyama, K.; Tateyama, Y. Cation Mixing Properties toward Co Diffusion at the LiCoO2 Cathode/Sulfide Electrolyte Interface in a Solid-State Battery. ACS Appl. Mater. Interfaces 2017, 9, 286– 292, DOI: 10.1021/acsami.6b0843533Cation Mixing Properties toward Co Diffusion at the LiCoO2 Cathode/Sulfide Electrolyte Interface in a Solid-State BatteryHaruyama, Jun; Sodeyama, Keitaro; Tateyama, YoshitakaACS Applied Materials & Interfaces (2017), 9 (1), 286-292CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)All-solid-state Li-ion batteries (ASS-LIBs) are expected to be the next-generation battery, however, their large interfacial resistance hinders their widespread application. To understand and resolve the possible causes of this resistance, we examd. mutual diffusion properties of the cation elements at LiCoO2 (LCO) cathode/β-Li3PS4 (LPS) solid electrolyte interface as a representative system as well as the effect of a LiNbO3 buffer layer by first-principles calcns. Evaluating energies of exchanging ions between the cathode and the electrolyte, we found that the mixing of Co and P is energetically preferable to the unmixed states at the LCO/LPS interface. We also demonstrated that the interposition of the buffer layer suppresses such mixing because the exchange of Co and Nb is energetically unfavorable. Detailed analyses of the defect levels and the exchange energies by using the individual bulk crystals as well as the interfaces suggest that the lower interfacial states in the energy gap can make a major contribution to the stabilization of the Co - P exchange, although the anion bonding preference of Co and P as well as the electrostatic interactions may have effects as well. Finally, the Co - P exchanges induce interfacial Li sites with low chem. potentials, which enhance the growth of the Li depletion layer. These atomistic understandings can be meaningful for the development of ASS-LIBs with smaller interfacial resistances.
- 34Leung, K.; Leenheer, A. How Voltage Drops Are Manifested by Lithium Ion Configurations at Interfaces and in Thin Films on Battery Electrodes. J. Phys. Chem. C 2015, 119, 10234– 10246, DOI: 10.1021/acs.jpcc.5b0164334How Voltage Drops Are Manifested by Lithium Ion Configurations at Interfaces and in Thin Films on Battery ElectrodesLeung, Kevin; Leenheer, AndrewJournal of Physical Chemistry C (2015), 119 (19), 10234-10246CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)Battery electrode surfaces are generally coated with electronically insulating solid films of thickness 1-50 nm. Both electrons and Li+ can move at the electrode-surface film interface in response to the voltage, which adds complexity to the "elec. double layer" (EDL). We apply D. Functional Theory (DFT) to investigate how the applied voltage is manifested as changes in the EDL at at. length scales, including charge sepn. and interfacial dipole moments. Illustrating examples include Li3PO4, Li2CO3, and LixMn2O4 thin films on Au(111) surfaces under ultrahigh vacuum conditions. Adsorbed org. solvent mols. can strongly reduce voltages predicted in vacuum. We propose that manipulating surface dipoles, seldom discussed in battery studies, may be a viable strategy to improve electrode passivation. We also distinguish the computed potential governing electrons, which is the actual or instantaneous voltage, and the "lithium cohesive energy"-based voltage governing Li content widely reported in DFT calcns., which is a slower-responding self-consistency criterion at interfaces. This distinction is crit. for a comprehensive description of electrochem. activities on electrode surfaces, including Li+ insertion dynamics, parasitic electrolyte decompn., and electrodeposition at overpotentials.
- 35Wang, Y.; Lv, J.; Zhu, L.; Ma, Y. Crystal Structure Prediction via Particle-Swarm Optimization. Phys. Rev. B: Condens. Matter Mater. Phys. 2010, 82, 094116, DOI: 10.1103/PhysRevB.82.09411635Crystal structure prediction via particle-swarm optimizationWang, Yanchao; Lv, Jian; Zhu, Li; Ma, YanmingPhysical Review B: Condensed Matter and Materials Physics (2010), 82 (9), 094116/1-094116/8CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)A method is developed for crystal structure prediction from scratch through particle-swarm optimization (PSO) algorithm within the evolutionary scheme. PSO technique is different with the genetic algorithm and has apparently avoided the use of evolution operators (e.g., crossover and mutation). The approach is based on an efficient global minimization of free-energy surfaces merging total-energy calcns. via PSO technique and requires only chem. compns. for a given compd. to predict stable or metastable structures at given external conditions (e.g., pressure). A particularly devised geometrical structure parameter which allows the elimination of similar structures during structure evolution was implemented to enhance the structure search efficiency. The application of designed variable unit-cell size technique has greatly reduced the computational cost. Moreover, the symmetry constraint imposed in the structure generation enables the realization of diverse structures, leads to significantly reduced search space and optimization variables, and thus fastens the global structure convergence. The PSO algorithm was successfully applied to the prediction of many known systems (e.g., elemental, binary, and ternary compds.) with various chem.-bonding environments (e.g., metallic, ionic, and covalent bonding). The high success rate demonstrates the reliability of this methodol. and illustrates the promise of PSO as a major technique on crystal structure detn.
- 36Wang, Y.; Lv, J.; Zhu, L.; Ma, Y. CALYPSO: A Method for Crystal Structure Prediction. Comput. Phys. Commun. 2012, 183, 2063– 2070, DOI: 10.1016/j.cpc.2012.05.00836CALYPSO: A method for crystal structure predictionWang, Yanchao; Lv, Jian; Zhu, Li; Ma, YanmingComputer Physics Communications (2012), 183 (10), 2063-2070CODEN: CPHCBZ; ISSN:0010-4655. (Elsevier B.V.)The authors have developed a software package CALYPSO (Crystal structure Anal. by Particle Swarm Optimization) to predict the energetically stable/metastable crystal structures of materials at given chem. compns. and external conditions (e.g., pressure). The CALYPSO method is based on several major techniques (e.g. particle-swarm optimization algorithm, symmetry constraints on structural generation, bond characterization matrix on elimination of similar structures, partial random structures per generation on enhancing structural diversity, and penalty function, etc.) for global structural minimization from scratch. All of these techniques are crit. to the prediction of global stable structure. The authors have implemented these techniques into the CALYPSO code. Testing of the code on many known and unknown systems shows high efficiency and the highly successful rate of this CALYPSO method. The authors focus on descriptions of the implementation of CALYPSO code and why it works.
- 37Gao, B.; Gao, P.; Lu, S.; Lv, J.; Wang, Y.; Ma, Y. Interface Structure Prediction via CALYPSO Method. Sci. Bull. 2019, 64, 301– 309, DOI: 10.1016/j.scib.2019.02.00937Interface structure prediction via CALYPSO methodGao, Bo; Gao, Pengyue; Lu, Shaohua; Lv, Jian; Wang, Yanchao; Ma, YanmingScience Bulletin (2019), 64 (5), 301-309CODEN: SBCUA5; ISSN:2095-9281. (Elsevier B.V.)The atomistic structures of solid-solid interfaces are of fundamental interests for understanding phys. properties of interfacial materials. However, detn. of interface structures faces a substantial challenge, both exptl. and theor. Here, we propose an efficient method for predicting interface structures via the generalization of our inhouse developed CALYPSO method for structure prediction. We devised a lattice match toolkit that allows us to automatically search for the optimal lattice-matched superlattice for construction of the interface structures. In addn., bonding constraints (e.g., constraints on interat. distances and coordination nos. of atoms) are imposed to generate better starting interface structures by taking advantages of the known bonding environment derived from the stable bulk phases. The interface structures evolve by following interfacially confined swarm intelligence algorithm, which is known to be efficient for exploration of potential energy surface. The method was validated by correctly predicting a no. of known interface structures with only given information of two parent solids. The application of the developed method leads to prediction of two unknown grain boundary (GB) structures (r-GB and p-GB) of rutile TiO2 Σ5(2 1 0) under an O reducing atm. that contained Ti3+ as the result of O defects. Further calcns. revealed that the intrinsic band gap of p-GB is reduced to 0.7 eV owing to substantial broadening of the Ti-3d interfacial levels from Ti3+ centers. Our results demonstrated that introduction of grain boundaries is an effective strategy to engineer the electronic properties and thus enhance the visible-light photoactivity of TiO2.
- 38Qian, D.; Hinuma, Y.; Chen, H.; Du, L.-S.; Carroll, K. J.; Ceder, G.; Grey, C. P.; Meng, Y. S. Electronic Spin Transition in Nanosize Stoichiometric Lithium Cobalt Oxide. J. Am. Chem. Soc. 2012, 134, 6096– 6099, DOI: 10.1021/ja300868e38Electronic Spin Transition in Nanosize Stoichiometric Lithium Cobalt OxideQian, Danna; Hinuma, Yoyo; Chen, Hailong; Du, Lin-Shu; Carroll, Kyler J.; Ceder, Gerbrand; Grey, Clare P.; Meng, Ying S.Journal of the American Chemical Society (2012), 134 (14), 6096-6099CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)A change in the electronic spin state of the surfaces relevant to Li (de)intercalation of nanosized stoichiometric LiCo(III)O2 from low-spin to intermediate and high spin was obsd. for the 1st time. These surfaces are relevant for Li (de)intercalation. From DFT calcns. with Hubbard U correction, the surface energies of the layered Li Co oxide can be lowered as a consequence of the spin change. The crystal field splitting of Co d orbitals is modified at the surface due to missing Co-O bonds. The electronic spin transition also has an impact on Co(III)-Co(IV) redox potential, as revealed by the change in the Li (de)intercalation voltage profile in a Li half cell.
- 39Yang, Y.; Wu, Q.; Cui, Y.; Chen, Y.; Shi, S.; Wang, R.-Z.; Yan, H. Elastic Properties, Defect Thermodynamics, Electrochemical Window, Phase Stability, and Li+ Mobility of Li3PS4: Insights from First-Principles Calculations. ACS Appl. Mater. Interfaces 2016, 8, 25229– 25242, DOI: 10.1021/acsami.6b0675439Elastic Properties, Defect Thermodynamics, Electrochemical Window, Phase Stability, and Li+ Mobility of Li3PS4: Insights from First-Principles CalculationsYang, Yanhan; Wu, Qu; Cui, Yanhua; Chen, Yongchang; Shi, Siqi; Wang, Ru-Zhi; Yan, HuiACS Applied Materials & Interfaces (2016), 8 (38), 25229-25242CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)The improved ionic cond. (1.64 × 10-4 S cm-1 at room temp.) and excellent electrochem. stability of nanoporous β-Li3PS4 make it one of the promising candidates for rechargeable all-solid-state lithium-ion battery electrolytes. Here, elastic properties, defect thermodn., phase diagram, and Li+ migration mechanism of Li3PS4 (both γ and β phases) are examd. via the first-principles calcns. Results indicate that both γ- and β-Li3PS4 phases are ductile while γ-Li3PS4 is harder under vol. change and shear stress than β-Li3PS4. The electrochem. window of Li3PS4 ranges from 0.6 to 3.7 V, and thus the exptl. excellent stability (>5 V) is proposed due to the passivation phenomenon. The dominant diffusion carrier type in Li3PS4 is identified over its electrochem. window. In γ-Li3PS4 the direct-hopping of Lii+ along the [001] is energetically more favorable than other diffusion processes, whereas in β-Li3PS4 the knock-off diffusion of Lii+ along the [010] has the lowest migration barrier. The ionic cond. is evaluated from the concn. and the mobility calcns. using the Nernst-Einstein relationship and compared with the available exptl. results. According to our calcd. results, the Li+ prefers to transport along the [010] direction. It is suggested that the enhanced ionic cond. in nanostructured β-Li3PS4 is due to the larger possibility of contiguous (010) planes provided by larger nanoporous β-Li3PS4 particles. By a series of motivated and closely linked calcns., we try to provide a portable method, by which researchers could gain insights into the physicochem. properties of solid electrolyte.
- 40Sanna, S.; Schmidt, W. G. Lithium Niobate X -Cut, Y -Cut, and Z -Cut Surfaces from Ab Initio Theory. Phys. Rev. B: Condens. Matter Mater. Phys. 2010, 81, 214116, DOI: 10.1103/PhysRevB.81.21411640Lithium niobate X-cut, Y-cut, and Z-cut surfaces from ab initio theorySanna, Simone; Schmidt, Wolf GeroPhysical Review B: Condensed Matter and Materials Physics (2010), 81 (21), 214116/1-214116/11CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)D.-functional theory calcns. of the LiNbO3 (2110), (1100), and (0001) surfaces, commonly referred to as X, Y, and Z cuts, are presented. In case of the Z cut, we find a pronounced dependence of the surface structure and stoichiometry on the direction of the ferroelec. polarization. In contrast, the influence of the chem. potentials of the surface constituents is limited. Rather electrostatics governs the surface stability. Different from the Z cut, the stoichiometry of the X cut and Y cut is clearly dependent on the prepn. conditions. The surface charge obsd. for the nominal nonpolar Y cut is traced back to the formation of a strong surface dipole.
- 41Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 1996, 77, 3865– 3868, DOI: 10.1103/PhysRevLett.77.386541Generalized gradient approximation made simplePerdew, John P.; Burke, Kieron; Ernzerhof, MatthiasPhysical Review Letters (1996), 77 (18), 3865-3868CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)Generalized gradient approxns. (GGA's) for the exchange-correlation energy improve upon the local spin d. (LSD) description of atoms, mols., and solids. We present a simple derivation of a simple GGA, in which all parameters (other than those in LSD) are fundamental consts. Only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked. Improvements over PW91 include an accurate description of the linear response of the uniform electron gas, correct behavior under uniform scaling, and a smoother potential.
- 42Kresse, G.; Joubert, D. From Ultrasoft Pseudopotentials to the Projector Augmented-Wave Method. Phys. Rev. B: Condens. Matter Mater. Phys. 1999, 59, 1758– 1775, DOI: 10.1103/PhysRevB.59.175842From ultrasoft pseudopotentials to the projector augmented-wave methodKresse, G.; Joubert, D.Physical Review B: Condensed Matter and Materials Physics (1999), 59 (3), 1758-1775CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)The formal relationship between ultrasoft (US) Vanderbilt-type pseudopotentials and Blochl's projector augmented wave (PAW) method is derived. The total energy functional for US pseudopotentials can be obtained by linearization of two terms in a slightly modified PAW total energy functional. The Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional. A simple way to implement the PAW method in existing plane-wave codes supporting US pseudopotentials is pointed out. In addn., crit. tests are presented to compare the accuracy and efficiency of the PAW and the US pseudopotential method with relaxed-core all-electron methods. These tests include small mols. (H2, H2O, Li2, N2, F2, BF3, SiF4) and several bulk systems (diamond, Si, V, Li, Ca, CaF2, Fe, Co, Ni). Particular attention is paid to the bulk properties and magnetic energies of Fe, Co, and Ni.
- 43Blöchl, P. E. Projector Augmented-Wave Method. Phys. Rev. B: Condens. Matter Mater. Phys. 1994, 50, 17953– 17979, DOI: 10.1103/PhysRevB.50.1795343Projector augmented-wave methodBlochlPhysical review. B, Condensed matter (1994), 50 (24), 17953-17979 ISSN:0163-1829.There is no expanded citation for this reference.
- 44Anisimov, V. I.; Zaanen, J.; Andersen, O. K. Band Theory and Mott Insulators: Hubbard U Instead of Stoner I. Phys. Rev. B: Condens. Matter Mater. Phys. 1991, 44, 943– 954, DOI: 10.1103/PhysRevB.44.94344Band theory and Mott insulators: Hubbard U instead of Stoner IAnisimov, V. I.; Zaanen, Jan; Andersen, Ole K.Physical Review B: Condensed Matter and Materials Physics (1991), 44 (3), 943-54CODEN: PRBMDO; ISSN:0163-1829.The authors propose a form for the exchange-correlation potential in local-d. band theory, appropriate to Mott insulators. The idea is to use the "constrained-local-d.-approxn." Hubbard parameter U as the quantity relating the single-particle potentials-to the magnetic- (and orbital-) order parameters. The authors' energy functional is that of the local-d. approxn. plus the mean-field approxn. to the remaining part of the U term. They argue that such a method should make sense, if one accepts the Hubbard model and the success of constrained-local-d.-approxn. parameter calcns. By using this ab initio scheme, they find that all late-3d-transition-metal monoxides, as well as the parent compds. of the high-Tc compds., are large-gap magnetic insulators of the charge-transfer type. Further, the method predicts that LiNiO2 is a low-spin ferromagnet and NiS a local-moment p-type metal. The present version of the scheme fails for the early-3d-transition-metal monoxides and for the late 3d transition metals.
- 45Zhou, F.; Cococcioni, M.; Marianetti, C. A.; Morgan, D.; Ceder, G. First-Principles Prediction of Redox Potentials in Transition-Metal Compounds with LDA+U. Phys. Rev. B: Condens. Matter Mater. Phys. 2004, 70, 235121, DOI: 10.1103/PhysRevB.70.23512145First-principles prediction of redox potentials in transition-metal compounds with LDA+UZhou, F.; Cococcioni, M.; Marianetti, C. A.; Morgan, D.; Ceder, G.Physical Review B: Condensed Matter and Materials Physics (2004), 70 (23), 235121/1-235121/8CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)First-principles calcns. within the local d. approxn. (LDA) or generalized gradient approxn. (GGA), though very successful, are known to underestimate redox potentials, such as those at which lithium intercalates in transition metal compds. We argue that this inaccuracy is related to the lack of cancellation of electron self-interaction errors in LDA/GGA and can be improved by using the DFT + U method with a self-consistent evaluation of the U parameter. We show that, using this approach, the exptl. lithium intercalation voltages of a no. of transition metal compds., including the olivine LixMPO4 (M = Mn, Fe Co, Ni), layered LixMO2 (x = Co, Ni) and spinel-like LixM2O4 (M = Mn, Co), can be reproduced accurately.
- 46Ohta, N.; Takada, K.; Sakaguchi, I.; Zhang, L.; Ma, R.; Fukuda, K.; Osada, M.; Sasaki, T. LiNbO3-Coated LiCoO2 as Cathode Material for All Solid-State Lithium Secondary Batteries. Electrochem. Commun. 2007, 9, 1486– 1490, DOI: 10.1016/j.elecom.2007.02.00846LiNbO3-coated LiCoO2 as cathode material for all solid-state lithium secondary batteriesOhta, Narumi; Takada, Kazunori; Sakaguchi, Isao; Zhang, Lianqi; Ma, Renzhi; Fukuda, Katsutoshi; Osada, Minoru; Sasaki, TakayoshiElectrochemistry Communications (2007), 9 (7), 1486-1490CODEN: ECCMF9; ISSN:1388-2481. (Elsevier B.V.)The enhancement of the high-rate capabilities for solid-state Li secondary batteries is reported. A nanometer thick LiNbO3 layer was interposed between LiCoO2 and the solid sulfide electrolyte as buffer layer. This decreased the interfacial resistance in the cathode and enhanced the high-rate capabilities of the batteries - this can enable design of Li secondary batteries free from safety issues.
- 47Fu, L.; Chen, C.-C.; Samuelis, D.; Maier, J. Thermodynamics of Lithium Storage at Abrupt Junctions: Modeling and Experimental Evidence. Phys. Rev. Lett. 2014, 112, 208301, DOI: 10.1103/physrevlett.112.20830147Thermodynamics of lithium storage at abrupt junctions: modeling and experimental evidenceFu, Lijun; Chen, Chia-Chin; Samuelis, Dominik; Maier, JoachimPhysical Review Letters (2014), 112 (20), 208301/1-208301/5, 5 pp.CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)We present the thermodn. modeling and exptl. evidence of the occurrence of lithium storage at abrupt junctions, which describes the transition from an electrostatic capacitor to a chem. capacitor. In both Ru:Li2O and Ni:LiF systems, the functionalities and extd. parameters are in good agreement with the thermodn. model, based on the dependence of the storage capacity on open-circuit voltage. Moreover, it is set out that a complete understanding of a conventional storage mechanism requires unifying both the space charge and bulk storage for a nanocryst. electroactive electrode.
Supporting Information
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.0c19091.
Lattice parameters calculated in our work and identified in experiments of LCO, LPS, and LNO, selected superlattices for LCO(104)/LNO(11̅0), and LNO(11̅0)/LPS(010) interfaces singled out using the lattice matching algorithm in the CALYPSO methodology, interface formation energies of energetically favorable structures of LCO(104)/LPS(010) interfaces, calculated EF(interf) – ηe–(interf), ηLi(interf), Vi and Ve in the LCO(104)/LPS(010), LCO(104)/LNO(11̅0), and LNO(11̅0)/LPS(010) interfaces, calculated ηLi(bulk) and ηe–(bulk) in LCO, LPS and LNO bulks, predicted metastable structures of the LCO(104)/LNO(11̅0) interface, predicted metastable structures of the LNO(11̅0)/LPS(010) interface, calculated ηLi(interf) in the IFpristine and IFCo–P,O–S of the LCO(104)/LPS(010) interface, calculated layer-decomposed PDOSs for IFpristine and IFCo–P,O–S of the LCO(104)/LPS(010) interface, calculated the charge difference and its average value over the plane parallel to the interface in the IFpristine of LCO(104)/LNO(11̅0) interface, schematic illustrations of the ηLi+ and ηe– in the bulk and interface models for LCO(104)/LPS(010), LCO(104)/LNO(11̅0) and LNO(11̅0)/LPS(010) interfaces (PDF)
Terms & Conditions
Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.